4-(N,N-dialkylamino)aniline compounds, photographic processing composition containing the same and color image-forming method

ABSTRACT

Disclosed are 4-(N,N-dialkylamino)aniline compounds having a 4-N substituent which is a polyethyleneoxy group and which forms a condensed ring with benzene ring, such as aniline compounds having the following structure, a processing composition containing such a compound and a method for forming a color image with the processing solution. The aniline compound is useful as a color developing agent capable of having a low fog density and sufficient yellow and cyan image densities and suitable for the rapid process.   &lt;IMAGE&gt;    &lt;IMAGE&gt;    &lt;IMAGE&gt;

BACKGROUND OF THE INVENTION

The present invention relates to 4-(N,N-dialkylamino)aniline compoundshaving a 4-N substituent which is a polyethyleneoxy group and whichforms a condensed ring with benzene ring, a processing compositioncontaining such a compound and a method for forming a color image withthe processing solution.

4-(N,N-dialkylamino)aniline compounds are useful as a developing agentfor a silver halide color photographic material and they are describedin, for example, Japanese Patent Unexamined Published Application(hereinafter referred to as "J. P. KOKAI") No. Hei 5-257248, 6-161061and 7-36162.

As mini-labs for processing photosensitive materials within the shopsand the amount of color negative films used in the field of news photosare increasing recently, the demand for completion of the developmentprocess in a shorter time to immediately provide the prints to thecustomers or to immediately place the photo in newspapers or the like israpidly increasing. The demand for reduction of the processing time isbecoming more and more eager in processing color negative films, sincethe time necessitated therefor is longer than that necessitated forprocessing color papers.

For the reduction of the time necessitated for the color developmentstep in the processing steps, J. P. KOKAI No. Hei 4-45440 discloses amethod wherein tetrahydroquinoline or a dihydroindole derivative is usedas the color developing agent. The use of such a compound as the colordeveloping agent is also described in U.S. Pat. Nos. 2,196,739 and2,566,259. In particular, it is described in J. P. KOKAI No. Hei 4-45440that the time necessitating for the color developing step can be reducedby using such a compound as the color developing agent even in colorphotographic photosensitive materials mainly comprising a silverbromoiodide emulsion such as color negative films. Further, it isdescribed in European Patent No. 670,312A1 that when at lease one ofthree carbon atoms forming the propylene chain of tetrahydroquinolineskeleton is free from hydrogen atom, the fog density is lowered.

However, it was found that the development of a photosensitive materialfor color photography with one of the compounds described in thesespecifications has some defects. Namely, since the image density in theunexposed part is high to cause a fog, the yellow and cyan imagedensities are insufficient as compared with the magenta image density inthe exposed part, and the three-colors are not well balanced.

Polyethyleneoxy groups having two or more repeating units are notdescribed in the description or in the examples of the compounds as a4-N substituent of a tetrahydroquinoline compound or dihydroindolecompound in the above-described J. P. KOKAI No. Hei 4-45440, U.S. Pat.Nos. 2,196,739 and 2,566,259 and European Patent No. 670,312A1. Not onlyin the compounds usable as the developing agent for silver halide colorphotographic materials but also in known 4-(N,N-dialkylamino)anilinecompounds in which a 4-N substituent is capable of forming a condensedring with a benzene ring such as the trahydroquinoline compounds anddihydroindole compounds, there are no compounds having a polyethyleneoxygroup having two or more repeating units as N-substituent.

SUMMARY OF THE INVENTION

An object of the present invention is to provide4-(N,N-dialkylamino)aniline compounds wherein the 4-N substituent formsa condensed ring with the benzene ring.

Another object of the present invention is to provide a color developingagent usable for silver halide color photographic materials.

Another object of the present invention is to provide a processingsolution for silver halide color photographic photosensitive materials,which contains the developing agent.

Another object of the present invention is to provide a colorimage-forming method with the developing agent.

Another object of the present invention is to provide a color developingagent capable of having a low fog density and sufficient yellow and cyanimage densities and suitable for the rapid process.

Another object of the present invention is to provide a processingcomposition containing the developing agent and useful for processing asilver halide color photographic photosensitive material.

Another object of the present invention is to provide a colorimage-forming method.

Another object of the invention is to provide a new compound expectedfor use as a starting material for dyes, medicines and agriculturalchemicals.

These and other objects of the present invention will be apparent fromthe following description and examples.

The above-described problems have been solved by:

(1) aniline compounds represented by the following general formula (I):##STR2## wherein R¹ represents a hydrogen atom or substituent, R²represents a substituent, Z represents a substituted or unsubstitutedethylene group or substituted or unsubstituted trimethylene group, nrepresents an integer of 2 to 8, and m represents 0 or an integer of 1to 3, and when m is 2 or larger, R² 's may be the same or different fromeach other,

(2) a color photographic processing composition comprising at least oneof the compounds described in item (1), and

(3) a color image-forming method which comprises developing animage-exposed silver halide color photographic photosensitive materialin the presence of at least one of the compounds described in item (1).

Although the compounds of the present invention are included in theclaims of the above-described J. P. KOKAI No. Hei 4-45440 and EuropeanPatent No. 670,312A1, the specifications of them are completely silenton the specific compounds corresponding to the color developing agent ofthe present invention. Therefore, it is impossible to know the structureand properties of the compounds of the present invention from thespecifications of them.

The 4-(N,N-dialkylamino)aniline compound in which the polyethyleneoxygroup as the 4-N substituent forms a condensed ring with the benzenering is expected to be usable as an intermediate for dyes for dyeingkeratin fibers such as human hair and also as a starting material formedicines and agricultural chemicals.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The detailed description will be made on the general formula (I).

R¹ represents a hydrogen atom or substituent having 1 to 20 carbonatoms, preferably 1 to 8 carbon atoms and more preferably 1 carbon atom.Examples of the substituents include alkyl group (preferably thosehaving 1 to 15 carbon atoms such as methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-pentadecyl,isopropyl, sec-butyl, isobutyl, t-butyl, 3-pentyl, 2-methylbutyl,isopentyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexylmethyl, t-pentyl and di-t-octyl groups), aryl groups(preferably those having 6 or 7 carbon atoms such as phenyl andm-hydroxyphenyl groups), heterocyclic groups (preferably 5-membered or6-membered saturated or unsaturated heterocyclic groups having 1 to 5carbon atoms and at least one oxygen, nitrogen or sulfur atom, such as2-furyl, 2-thienyl, 2-pyrimidinyl, imidazolyl and pyrazolyl groups),alkoxycarbonyl groups (preferably those having 1 to 7 carbon atoms suchas methoxycarbonyl and t-butoxycarbonyl groups), silyl groups(preferably those having 3 to 7 carbon atoms such as trimethylsilyl,isopropyldiethylsilyl and t-butyldimethylsilyl groups), aryloxycarbonylgroups (preferably those having 1 to 7 carbon atoms such asphenoxycarbonyl and 3-hydroxyphenoxycarbonyl groups) and acyl groups(preferably those having 1 to 7 carbon atoms such as acetyl, benzoyl and4-hydroxybenzoyl groups).

R¹ is preferably that selected from among hydrogen atom, alkyl groups,aryl groups and heterocyclic groups. Among them, hydrogen atom or alkylgroup is more preferred.

Preferred examples of R¹ include hydrogen atom, and methyl, ethyl,n-propyl, n-butyl, n-pentyl, phenyl, imidazolyl and pyrazolyl groups.Among them, hydrogen atom and alkyl group having 1 to 3 carbon atoms (inparticular, methyl, ethyl and n-propyl groups) are more preferred.Hydrogen atom and methyl groups are particularly preferred.

R² represents a substituent having 0 to 20 carbon atoms, preferably 0 to8 carbon atoms, more preferably 1 to 8 carbon atoms, most preferably 1to 3 carbon atoms. Examples of the substituents include hydroxyl group,halogen atoms (such as fluorine and chlorine atoms), alkyl groups(preferably those having 1 to 8 carbon atoms such as methyl, ethyl,n-propyl, i-propyl, n-butyl, t-butyl, t-pentyl, di-t-octyl,hydroxymethyl and 1,3-dihydroxy-2-propyl groups), aryl groups(preferably those having 6 or 7 carbon atoms such as phenyl andm-hydroxyphenyl groups), heterocyclic groups (preferably 5-membered or6-membered saturated or unsaturated heterocyclic groups having 1 to 5carbon atoms and at least one oxygen, nitrogen or sulfur atom, such as2-furyl, 2-thienyl, 2-pyrimidinyl, imidazolyl and pyrazolyl groups),alkoxy groups (preferably those having 1 to 8 carbon atoms such asmethoxy, ethoxy, i-propoxy, 2-hydroxyethoxy, 2-methanesulfonylethoxy,2-(2-hydroxyethoxy)ethoxy and 2- 2-(2-hydroxyethoxy)ethoxy!ethoxygroups}, aryloxy groups (preferably those having 6 or 7 carbon atomssuch as phenoxy and p-hydroxyphenoxy groups), carboxyl group, acylaminogroups (preferably those having 1 to 7 carbon atoms such as acetamido,2-methoxypropionamido and p-hydroxybenzoylamido groups), alkylaminogroups (preferably those having 1 to 7 carbon atoms such asdimethylamino, diethylamino and 2-hydroxyethylamino groups), anilinogroups (preferably those having 6 or 7 carbon atoms such as anilino,m-nitroanilino and m-hydroxyanilino groups), ureido groups (preferablythose having 1 to 7 carbon atoms such as ureido, methylureido,N,N-dimethylureido and 2-methanesulfonamidoethylureido groups),sulfamoylamino groups (preferably those having 0 to 7 carbon atoms suchas dimethylsulfamoylamino, methylsulfamoylamino and2-methoxyethylsulfamoylamino groups), alkylthio groups (preferably thosehaving 1 to 7 carbon atoms such as methylthio, ethylthio and benzylthiogroups), arylthio groups (preferably those having 6 or 7 carbon atomssuch as phenylthio, 2-carboxyphenylthio and 4-hydroxyphenylthio groups),alkoxycarbonylamino groups (preferably those having 2 to 7 carbon atomssuch as methoxycarbonylamino, ethoxycarbonylamino and3-methanesulfonylpropoxycarbonylamino groups), sulfonylamino groups(preferably those having 1 to 7 carbon atoms such as methanesulfonamido,p-toluenesulfonamido and 2-methoxyethanesulfonamido groups), carbamoylgroups (preferably those having 1 to 7 carbon atoms such as carbamoyl,N,N-dimethylcarbamoyl and N-ethylcarbamoyl groups), sulfamoyl groups(preferably those having 0 to 7 carbon atoms such as sulfamoyl,dimethylsulfamoyl and ethylsulfamoyl groups), sulfonyl groups(preferably aliphatic sulfonyl groups having 1 to 5 carbon atoms andaromatic sulfonyl groups having 6 or 7 carbon atoms such asmethanesulfonyl, ethanesulfonyl and 2-chloroethanesulfonyl groups),alkoxycarbonyl groups (preferably those having 1 to 7 carbon atoms suchas methoxycarbonyl and t-butoxycarbonyl groups), heterocyclic oxy groups(preferably five-membered or six-membered, saturated or unsaturatedheterocyclic oxy groups having 1 to 5 carbon atoms and at least oneoxygen, nitrogen or sulfur atom, wherein the number of the hetero atomand the variety of the element constituting the ring may be one or more,such as 1-phenyltetrazole-5-yl-oxy, 2-tetrahydropyranyloxy and2-pyridyloxy groups), azo groups (preferably those having 1 to 7 carbonatoms such as phenylazo, 2-hydroxyphenylazo and 4-sulfophenylazogroups), acyloxy groups (preferably those having 1 to 7 carbon atomssuch as acetoxy, benzoyloxy and 4-hydroxybutanoyloxy groups),carbamoyloxy groups (preferably those having 1 to 7 carbon atoms such asN,N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxygroups), silyl groups (preferably those having 3 to 7 carbon atoms suchas trimethylsilyl, isopropyldiethylsilyl and t-butyldimethylsilylgroups), silyloxy groups (preferably those having 3 to 7 carbon atomssuch as trimethylsilyloxy and triethylsilyloxy groups),aryloxycarbonylamino groups (preferably those having 7 carbon atoms suchas phenoxycarbonylamino and 4-hydroxyphenoxycarbonylamino groups), imidogroups (preferably those having 4 to 7 carbon atoms such asN-succinimido group), heterocyclic thio groups (five-membered orsix-membered, saturated or unsaturated heterocyclic thio groups having 1to 5 carbon atoms and at least one of oxygen, nitrogen and sulfur atoms,wherein the number of the hetero atom and variety of the elementconstituting the ring may be one or more, such as 2-benzothiazolylthioand 2-pyridylthio groups), sulfinyl groups (preferably those having 1 to7 carbon atoms such as methanesulfinyl, benzenesulfinyl andethanesulfinyl groups), phosphonyl groups (preferably those having 2 to7 carbon atoms such as methoxyphosphonyl, ethoxyphosphonyl andphenoxyphosphonyl groups), aryloxycarbonyl groups (preferably thosehaving 1 to 7 carbon atoms such as phenoxycarbonyl and3-hydroxyphenoxycarbonyl groups), and acyl groups (preferably thosehaving 1 to 7 carbon atoms such as acetyl, benzoyl and 4-hydroxybenzoylgroups).

R² is preferably a group selected from among alkyl, aryl, alkoxy,acylamino, ureido, sulfamoylamino, sulfonylamino, carbamoyl andsulfamoyl groups. Among them, alkyl, alkoxy, carbamoyl, sulfamoyl andureido groups are preferred, and alkyl and alkoxy groups areparticularly preferred.

Preferred examples of R² include methyl, ethyl, n-propyl, i-propyl,n-butyl, t-butyl, t-pentyl, di-t-octyl, hydroxymethyl,1,3-dihydroxy-2-propyl, phenyl, m-hydroxyphenyl, methoxy, ethoxy,i-propoxy, 2-hydroxyethoxy, 2-methanesulfonylethoxy,2-(2-hydroxyethoxy)ethoxy, 2- 2-(2-hydroxyethoxy)ethoxy!ethoxy),acetamido, 2-methoxypropionamido, p-hydroxybenzoylamido, ureido,methylureido, N,N-dimethylureido, 2-methanesulfonamidoethylureido,dimethylsulfamoylamino, methylsulfamoylamino,2-methoxyethylsulfamoylamino, methanesulfonamido, p-toluenesulfonamido,2-methoxyethanesulfonamido, carbamoyl, N,N-dimethylcarbamoyl,N-ethylcarbamoyl, sulfamoyl, dimethylsulfamoyl and ethylsulfamoylgroups. Among them, particularly preferred examples of R² are methyl,ethyl, n-propyl, i-propyl, t-butyl, methoxy, i-propoxy, acetamido,ureido, methylureido, N,N-dimethylureido, dimethylsulfamoylamino,methylsulfamoylamino, methanesulfonamido, carbamoyl,N,N-dimethylcarbamoyl, N-ethylcarbamoyl, sulfamoyl and dimethylsulfamoylgroups. Among them, an alkyl and alkoxy groups having 1 to 3 carbonatoms (in particular, methyl, ethyl, i-propyl, methoxy and i-propoxygroups) are the best.

Z represents a substituted or unsubstituted ethylene chain ortrimethylene chain having 2 to 20 carbon atoms, preferably 2 to 10carbon atoms and more preferably 2 to 6 carbon atoms. The substituentsare those in the range described above with reference to R². Preferredsubstituents include hydroxyl group, halogen atoms, and alkyl, alkoxy,carboxy, acylamino, alkylamino, ureido, sulfamoylamino,alkoxycarbonylamino, sulfonylamino, carbamoyl, sulfamoyl, sulfonyl,alkoxycarbonyl, acyloxy, carbamoyloxy and acyl groups. Among them,particularly preferred substituents are hydroxyl, alkyl, carboxyl,acylamino, ureido, alkoxycarbonylamino, sulfonylamino, carbamoyl,acyloxy and carbamoyloxy groups. Among them, hydroxy, alkyl and carboxylgroups are more preferable. Examples of Z include groups, in which thecarbon atom bonded to the nitrogen atom is in 1-position, such asethylene, 1-methylethylene, 2-methylethylene, 1,2-dimethylethylene,1,1,2-trimethylethylene, 1,2,2-trimethylethylene,1,1,2,2-tetramethylethylene, 2-hydroxymethylethylene, 2-hydroxyethylene,1-methyl-2-hydroxyethylene, 1,1,2-trimethyl-2-carboxyethylene,1,1,2,2-tetraethylethylene, trimethylene, 1,1-dimethyltrimethylene,2,2-dimethyltrimethylene, 3,3-dimethyltrimethylene,1,1,3-trimethyltrimethylene, 1,1,3-trimethyl-2-decyltrimethylene,1,1,3-triethyl-2-methyltrimethylene, 1,1-diethyltrimethylene,2,2-diethyltrimethylene, 3,3-diethyltrimethylene,1,1,2,2,3,3-hexaethyltrimethylene,1,1,3-trimethyl-3-carboxytrimethylene,1,1,3-trimethyl-2-hydroxytrimethylene,1,1-dimethyl-2-hydroxy-3-methylidenetrimethylene,1,1,3-trimethyl-2,3-dihydroxytrimethylene,1,1,3-trimethyl-2-aminotrimethylene,1,1,3-trimethyl-2-dimethylaminotrimethylene,1,1,3-trimethyl-2-bromotrimethylene,1,1,3-trimethyl-2-(N-pyrazolyl)trimethylene,1,1-dihydroxymethyl-3-methyltrimethylene,1,1-dimethyl-3-hydroxymethyltrimethylene,1,1-dimethyl-3-formyltrimethylene, 1,1-dimethyl-3-carboxytrimethylene,1,1-dimethyl-3-carbamoyltrimethylene,1,1-dimethyl-3-dimethylcarbamoyltrimethylene,1,1-dimethyl-3-hydroxymethyl-2,3-dihydroxytrimethylene and1,1-dimethyl-3-hydroxymethyl-2-hydroxytrimethylene. Among them,preferred examples include ethylene, 1-methylethylene, 2-methylethylene,1,2-dimethylethylene, 1,2,2-trimethylethylene,1,1,2,2-tetramethylethylene, 2-hydroxyethylene,1-methyl-2-hydroxyethylene, 1,1-dimethyltrimethylene,2,2-dimethyltrimethylene, 3,3-dimethyltrimethylene,1,1,3-trimethyltrimethylene, 1,1,3-triethyl-2-methyltrimethylene,1,1,3-trimethyl-2-hydroxytrimethylene,1,1,3-trimethyl-2,3-dihydroxytrimethylene,1,1-dimethyl-3-hydroxymethyltrimethylene and1,1-dimethyl-3-hydroxymethyl-2-hydroxytrimethylene. Among them,particularly preferred examples include ethylene, 1-methylethylene,2-methylethylene, 1,2-dimethylethylene, 1,1-dimethyltrimethylene,2,2-dimethyltrimethylene, 3,3-dimethyltrimethylene,1,1,3-trimethyltrimethylene, 1,1,3-trimethyl-2-hydroxytrimethylene and1,1-dimethyl-3-hydroxymethyltrimethylene.

It is preferable that n represents 2 to 5.

In a preferred combination of R¹, R², Z, n and m, R¹ represents ahydrogen atom or alkyl group, R² represents an alkyl or alkoxyl group, Zrepresents an ethylene chain or trimethylene chain, which may beunsubstituted or substituted with a hydroxyl, alkyl or carboxyl group,and which has 2 to 6 carbon atoms, n is an integer of 2 to 5 and m is 0or 1.

The most preferred compounds are represented by the following generalformula (I-a): ##STR3## wherein R¹ represents a hydrogen atom or alkylgroup having 1 to 3 carbon atoms, R²² represents a hydrogen atom, alkylor alkoxy group having 1 to 3 carbon atoms, Z represents a substitutedor unsubstituted ethylene group or substituted or unsubstitutedtrimethylene group, each group of which has 2 to 6 carbon atoms whereina substituent in the substituted ethylene group or substitutedtrimethylene group is selected from the group consisting of hydroxyl,alkyl and carboxyl groups, and n represents an integer of 2 to 5.

Examples of the compounds represented by the general formula (I) of thepresent invention are given below, which by no means limit theinvention. ##STR4##

Since the compounds of the general formula (I) are very unstable whenthey are stored in the form of the free amines, they are usuallyproduced and stored in the form of salts thereof with an inorganic ororganic acid, and they are converted into the free amines when they areto be used or, in particular, when they are to be added to theprocessing solution. The inorganic and organic acids used for formingthe salts with the compounds of the general formula (I) include, forexample, hydrochloric acid, sulfuric acid, phoshoric acid,p-toluenesulfonic acid, methanesulfonic acid andnaphthalene-1,5-disulfonic acid. Among these salts, salts with sulfuricacid, p-toluenesulfonic acid or naphthalene-1,5-disulfonic acid arepreferred. The salts with sulfuric acid is the most desirable.

The 4-(N,N-dialkylamino)aniline compounds can be synthesized accordingto a method described in, for example, Journal of the American ChemicalSociety, Vol. 73, p. 3100 (1951). They can be synthesized also bysynthesizing methods which will be described below and so on. ##STR5##

In the synthesis method, an alkyl group is introduced into the aminogroup of aniline forming the condensed ring with benzene. In particular,a polyethyleneoxy group is introduced thereinto at first by the reactionwith a polyethyleneoxy group-containing halide, or a polyethyleneoxygroup-containing alkyl or aryl-sulfonate. Then, the azo couplingreaction in the p-position of the amino group is conducted or a nitrosoor nitro group is introduced thereinto, and the obtained product isreduced by catalytic hydrogenation, reduction with zinc under acidicconditions or reduction with reducing iron to obtain the intendedproduct.

In the alkylation reaction, for example, 1 to 5 equivalents, preferably1 to 3 equivalents, of an alkyl halide (chloride, bromide or iodide),alkyl sulfonate (mesylate, tosylate or the like) or alkyl ester(acetate, benzoate or the like) is used as the alkylating agent foralkylating one equivalent of the compound; 1 to 5 equivalents,preferably 1 to 3 equivalents, of an organic base (such as triethylamineor diazabicycloundecene) or inorganic base (such as sodiumhydrogencarbonate, sodium carbonate, potassium carbonate, sodiumhydroxide or potassium hydroxide) is used for alkylating one equivalentof the compound; and the reaction is carried out without using anysolvent or in a solvent such as an amide solvent (e. g.N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone),sulfone solvent (e. g. sulfolane), sulfoxide solvent (e. g. dimethylsulfoxide), ureide solvent (e. g. tetramethylurea), ether solvent (e. g.dioxane) or alcohol solvent (e. g. isopropyl alcohol or butanol) in theabsence or presence of a catalyst (e. g. sodium iodide) at a reactiontemperature in the range of 0° to 200° C., preferably 80° to 170° C. fora reaction time in the range of 10 minutes to 72 hours, preferably 30minutes to 12 hours.

Then, azo coupling is conducted in the p-position of the amino group, ora nitroso group or nitro group is introduced thereinto. The azo couplingis conducted by, for example, converting unsubstituted or substitutedaniline into a diazonium salt thereof in the presence of an acid (aninorganic or organic acid such as hydrochloric acid, sulfuric acid,methanesulfonic acid or acetic acid) without using any solvent or inwater or an organic solvent (such as an alcohol solvent, e. g. methanol,ethanol or isopropyl alcohol; an amide solvent, e. g.N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone;a sulfone solvent, e. g. sulfolane; a sulfoxide solvent, e. g. dimethylsulfoxide; or ureido solvent, e. g. tetramethylurea) at a reactiontemperature in the range of -78° to 40° C., preferably -20° to 30° C.for a reaction time in the range of 5 minutes to 5 hours, preferably 5minutes to 1 hour; and then coupling 1 to 5 equivalents, preferably 1 to2 equivalents, of the obtained diazonium salt with an N,N-dialkylanilinein water or an organic solvent (such as an alcohol solvent, e. g.methanol, ethanol or isopropyl alcohol; amide solvent, e. g.N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone;sulfone solvent, e. g. sulfolane; sulfoxide solvent, e. g. dimethylsulfoxide; or ureide solvent, e. g. tetramethylurea) at a reactiontemperature in the range of -78° to 40° C., preferably -20° to 30° C.for a reaction time in the range of 5 minutes to 5 hours, preferably 5minutes to 1 hour. The coupling reaction is conducted preferably underweakly acidic to weakly basic conditions. The nitrosation reaction iscarried out by, for example, using 1 to 5 equivalents, preferably 1 to 2equivalents, of an organic nitrosating agent (such as isoamyl nitrite)or inorganic nitrosating agent (such as sodium nitrite) in the presenceof an acid (an inorganic or organic acid such as hydrochloric acid,sulfuric acid, methanesulfonic acid or acetic acid) without using anysolvent or in water or an organic solvent (such as an alcohol solvent,e. g. methanol, ethanol or isopropyl alcohol; an amide solvent, e. g.N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone;a sulfone solvent, e. g. sulfolane; a sulfoxide solvent, e. g. dimethylsulfoxide; or ureido solvent such as tetramethylurea) at a reactiontemperature in the range of -78° to 40° C., preferably -20° to 30° C.for a reaction time in the range of 5 minutes to 5 hours, preferably 5minutes to 1 hour. The nitration reaction is carried out by, forexample, using 1 to 5 equivalents, preferably 1 to 1. 5 equivalents, ofnitric acid in having a concentration in the range of 60 to 98% in theabsence or presence of an activating agent selected from among sulfuricacid, sulfuric anhydride, acetic anhydride or trifluoroacetic anhydridewithout using any solvent or in water or an organic solvent (such as analcohol solvent, e. g. methanol, ethanol or isopropyl alcohol; anorganic acid, e. g. acetic acid; an organic acid anhyride, e. g. aceticanhydride or trifluoroacetic anhydride; amide solvent, e. g.N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone;a sulfone solvent, e. g. sulfolane; a sulfoxide solvent, e. g. dimethylsulfoxide; or ureido solvent, e. g. tetramethylurea) at a reactiontemperature in the range of -78° to 100° C., preferably -20° to 30° C.for a reaction time in the range of 5 minutes to 5 hours, preferably 5minutes to 1 hour.

Finally, the reaction product is reduced by, for example, catalyticreduction with hydrogen, reduction with zinc under an acidic conditionor reduction with reduced iron to obtain the intended product. Forexample, the catalyltic reaction with hydrogen is conducted in thepresence of a catalyst (such as palladium/carbon or Raney nickel)without using any solvent or in water or an organic solvent (such as analcohol solvent, e. g. methanol, ethanol or isopropyl alcohol; an amidesolvent, e. g. N,N-dimethylacetamide, N,N-dimethylformamide or1-methyl-2-pyrrolidone; a sulfone solvent, e. g. sulfolane; a sulfoxidesolvent, e. g. dimethyl sulfoxide; or ureido solvent such astetramethylurea) at a reaction temperature in the range of 0° to 150°C., preferably 0° to 50° C. under a hydrogen pressure in the range of 1to 500 atm, preferably 1 to 200 atm for a reaction time in the range of5 minutes to 72 hours, preferably 1 to 8 hours. The reduction withreduced iron is conducted by, for example, using 4 to 10 equivalents,preferably 4 to 6 equivalents, of reduced iron and 0.0001 to 1equivalent, preferably 0.001 to 0.1 equivalent, of an acid (such as aninorganic acid, e. g. hydrochloric acid or sulfuric acid, or an organicacid, e. g. acetic acid or methanesulfonic acid) or an acid salt (suchas ammonium chloride, sodium chloride or sodium sulfate) singly or incombination of two or more of them without using any solvent or in wateror an organic solvent (such as an alcohol solvent, e. g. methanol,ethanol or isopropyl alcohol; an amide solvent, e. g.N,N-dimethylacetamide, N,N-dimethylformamide or 1-methyl-2-pyrrolidone;a sulfone solvent, e. g. sulfolane; a sulfoxide solvent, e. g. dimethylsulfoxide; or ureide solvent, e. g. tetramethylurea) at a reactiontemperature in the range of 0° to 150° C., preferably 50° to 100° C. fora reaction time in the range of 30 minutes to 72 hours, preferably 1 to8 hours. The reduction with zinc under an acidic condition is conductedby, for example, using 3 to 10 equivalents, preferably 3 to 6equivalents, of zinc powder in the presence of an acid (such as anorganic acid, e. g. acetic acid or methanesulfonic acid, or an inorganicacid, e. g. hydrochloric acid or sulfuric acid) without using anysolvent or in water or an organic solvent (such as an alcohol solvent,e. g. methanol, ethanol or isopropyl alcohol; an organic acid, e. g.acetic acid; an amide solvent e. g. N,N-dimethylacetamide,N,N-dimethylformamide or 1-methyl-2-pyrrolidone; a sulfone solvent, e.g. sulfolane; a sulfoxide solvent, e. g. dimethyl sulfoxide; ureidesolvent, e. g. tetramethylurea; or an organic acid solvent, e. g. aceticacid, propionic acid or methanesulfonic acid) at a reaction temperaturein the range of 0° to 150° C., preferably 0° to 100° C. for a reactiontime in the range of 5 minutes to 72 hours, preferably 30 minutes to 3hours.

The reaction product thus obtained is treated by an ordinaryafter-treatment method which is usually conducted after organicsynthesis reactions, and then purified if necessary. Namely, the productisolated from the reaction system is used without the purification orafter the purification by recrystallization, column chromatography orthe like, or by a combination of such processes. Alternatively, thereaction product can be poured into water or ice after the completion ofthe reaction followed by the distillation of the reaction solvent orwithout the distillation, the product is then neutralized, if necessary,and purified, if necessary, by one or a combination of therecrystallization, column chromatography, etc. before the use. Inanother embodiment, the reaction solvent is distilled off, if necessary,after the completion of the reaction, the reaction product is pouredinto water or ice, then neutralized if necessary and extracted with anorganic solvent, the obtained extract is purified, if necessary, bycrystallization and/or column chromatography before use.

Synthesis Examples of anilines forming a condensed ring with benzenering are given below. ##STR6##

The dihydroindole skeleton can be obtained by Fischer's indole synthesismethod from an arylhydrazine as shown above and then reducing theobtained indole compound or indolenine compound. ##STR7##

In another method, a hydroxymethyl group is introduced into the benzylring, this group is chlorinated and then a condensed ring is formed withthe amino group in the 2-position of the benzene ring according toJournal of the Organic Chemistry, Vol. 55, p. 580 (1990). ##STR8##

As for the formation of tetrahydroquinoline skeleton,2,2,4-trimethyltetrahydroquinoline can be obtained by dehydrationcondensation of aniline with acetone followed by reduction of theproduct by a method described on page 328 of Organic SynthesisCollective Volume III. ##STR9##

From N-allylaniline and zinc (II) chloride, a correspondingtetrahydroquinoline can be obtained by a method described in Journal ofJapanese Chemical Society, p. 1043 (1981). ##STR10##

Further, such a compound can be obtained by Friedel-Crafts reaction ofan α, β-unsaturated amide and the reduction of the amide by a methoddescribed in Journal of the American Chemical Society, Vol. 62, p. 778(1940).

Thus, various substituents can be introduced into the propylene chain ofthe tetrahydroquinoline structure by using the intermediate materialconstituting the basic skeleton. Some examples are given below.##STR11##

The description will be made on the use of the compounds of the presentinvention as color developing agent. The compound of the presentinvention can be used as the color developing agent either singly or incombination with other known p-phenylenediamine derivatives. Typicalexamples of the compounds usable in combination with the colordeveloping agent include the following compounds, which by no meanslimit them: N,N-diethyl-p-phenylenediamine (P-1),4-amino-3-methyl-N,N-diethylaniline (P-2),4-amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline (P-3),4-amino-N-ethyl-N-(2-hydroxyethyl)aniline (P-4),4-amino-3-methyl-N-ethyl-N-(2-hydroxyethyl)aniline (P-5),4-amino-3-methyl-N-ethyl-N-(2-methanesulfonamidoethyl)aniline (P-6),N-(2-amino-5-N,N-diethylaminophenylethyl)methane sulfonamide (P-7),N,N-dimethyl-p-phenylenediamine (P-8),4-amino-3-methyl-N-ethyl-N-(2-methoxyethyl)aniline (P-9),4-amino-3-methyl-N-ethyl-N-(4-hydroxybutyl) aniline (P-10), and4-amino-3-methyl-N-ethyl-N-(2-butoxyethyl)aniline (P-11). Among theabove-described p-phenylenediamine derivatives to be used for thecombination, particularly preferred are compounds P-3, P-5, P-6 andP-10. The p-phenylenediamine derivatives are usually used in the form oftheir salts such as sulfates, hydrochlorides, sulfites,p-toluenesulfonates, nitrates and naphthalene-1,5-disulfonates.

The processing composition may be in liquid form or solid form (such aspowdery, granular or tablet form).

These compounds are usable in combination of two or more of themdepending on the purpose. The aromatic primary amine developing agent isused in an amount of preferably about 0.001 to 0.2 mol, more preferably0.005 to 0.1 mol, per liter of the color developer.

In the color development with the compound of the present invention,this compound is incorporated into a processing solution or,alternatively, the compound or a precursor thereof is contained in aphotosensitive material so that the compound is formed to exhibit itseffect in the development process. In this case, the amount of thecompound is 1 to 30 parts, preferably 1 to 10 parts, more preferably 1to 4 parts, per part of the coupler.

The color developer may contain a compound for directly preserving theabove-described aromatic primary amine color developing agent, which isselected from among hydroxylamines described in J.P. KOKAI Nos. Sho63-5341, Sho 63-106655 and Hei 4-144446, hydroxamic acids described inJ.P. KOKAI No. Sho 63-43138, hydrazines and hydrazides described in J.P.KOKAI No. Sho 63-146041, phenols described in J.P. KOKAI Nos. Sho63-44657 and Sho 63-58443, α-hydroxyketones and α-aminoketones describedin J.P. KOKAI No. Sho 63-44656, and saccharides described in J.P. KOKAINo. Sho 63-36244. Such a compound can be used in combination withmonoamines described in J.P. KOKAI Nos. Sho 63-4235, 63-24254, 63-21647,63-146040, 63-27841 and 63-25654, diamines described in J.P. KOKAI Nos.Sho 63-30845, 63-14640 and 63-43139, polyamines described in J.P. KOKAINos. Sho 63-21647, 63-26655 and 63-44655, nitroxy radicals described inJ.P. KOKAI No. Sho 63-53551, alcohols described in J.P. KOKAI Nos. Sho63-43140 and 63-53549, oximes described in J.P. KOKAI No. Sho 63-56654and tertiary amines described in J.P. KOKAI No. Sho 63-239447. The colordeveloper may contain, if necessary, also a preservative such as metalsdescribed in J.P. KOKAI Nos. Sho 57-44148 and 57-53749, salicylic acidsdescribed in J.P. KOKAI No. Sho 59-180588, alkanolamines described inJ.P. KOKAI No. Sho 54-3582, polyethyleneimines described in J.P. KOKAINo. Sho 56-94349 and aromatic polyhydroxy compounds described in U.S.Pat. No. 3,746,544. Particularly when the hydroxylamines are used, theyare preferably used in combination with the above-describedalkanolamines or aromatic polyhydroxy compounds.

Particularly preferred preservatives are hydroxylamines represented bygeneral formula (I) given in J.P. KOKAI No. Hei 3-144446. Among them,compounds having methyl, ethyl, sulfo or carboxyl group are preferred.The preservative is used in an amount of 20 to 200 mmol, preferably 30to 150 mmol, per liter of the color developer.

The color developer for the photosensitive material for prints containspreferably 3.0×10⁻² to 1.5×10⁻¹ mol/l, particularly preferably 3.5×10⁻²to 1.0×10⁻¹ mol/l, of chlorine ion. When the chlorine ion concentrationis higher than 1.5×10⁻¹ mol/l or particularly higher than 1.0×10⁻¹mol/l, the development is retarded, which is against the object of thepresent invention, i.e. to rapidly attain the high maximum density and,on the contrary, a chlorine ion concentration of below 3.0×10⁻² mol/l isunsuitable for prevention of the fogging.

The color developer used in the present invention contains preferably0.5×10⁻⁵ to 1.0×10⁻³ mol/l, more preferably 3.0×10⁻⁵ to 5×10⁻⁴ mol/l ofbromine ion. When the bromine ion concentration is higher than 1×10⁻³mol/l, the development is retarded, and the maximum density andsensitivity are lowered and, on the contrary, when it is below 0.5×10⁻⁵mol/l, the fogging cannot be sufficiently prevented.

The chlorine ion and bromine ion can be directly added to the colordeveloper or they can be dissolved out of the photosensitive materialinto the color developer in the course of the development.

When the chlorine ion is directly added to the color developer, thechlorine ion-feeding substances include sodium chloride, potassiumchloride, ammonium chloride, lithium chloride, magnesium chloride andcalcium chloride. The chlorine ion can be fed from a fluorescentbrightener added to the color developer. The bromine ion-feedingsubstances include sodium bromide, potassium bromide, ammonium bromide,lithium bromide, calcium bromide and magnesium bromide.

When the chlorine ion or bromine ion is dissolved out of thephotosensitive material in the course of the development, such an ioncan be fed by an emulsion or another substance.

The color developer may further contain additives mentioned in theabove-described J.P. KOKAI No. Hei 3-144446. For example, a compoundselected from among carbonates, phosphates, borates and hydroxybenzoatesmentioned on page 9 of the specification thereof can be used as abuffering agent for maintaining pH. pH of the color developer is keptpreferably in the range of 9.0 to 12.5, more preferably in the range of9.5 to 11.5, with such a buffering agent.

Antifoggants usable herein are halide ions and organic antifoggantsmentioned on page 10 of that specification. Particularly when theconcentration of the color developing agent in the color developer is ashigh as 20 mmol/l or above or when the processing temperature is as highas 40° C. or above, a considerably high bromide ion concentration ispreferred. Namely, it is preferably 17 to 60 mmol/l. If necessary, theconcentration can be controlled in a preferred range by removing thehalogen with an ion exchange resin or ion exchange membrane.

The chelating agents preferably used herein are aminopolycarboxylicacids, aminopolyphosphonic acids, alkylphoshonic acids andphosphonocarboxylic acids. They are typified byethylenediaminetetraacetic acid, nitrilotriacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonicacid, nitrilo-N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N,N-tetramethylenephosphonic acid,ethylenediamine-di(o-hydroxyphenylacetic acid) and salts of them.Preferred chelating agents are biodegradable compounds such as thosementioned in J.P. KOKAI Nos. Sho 63-146998, 63-199295, 63-267750 and63-267751 and Hei 2-229146 and 3-186841, German Patent No. 3739610 andEuropean Patent No. 468325.

The color developer of the present invention may contain, if necessary,also a development restrainer such as a benzimidazole, benzothiazole ormercapto compound; a development accelerator such as a benzyl alcohol,polyethylene glycol, quaternary ammonium salt or amine; a dye-formingcoupler; a competitive coupler; an assistant developing agent such as1-phenyl-3-pyrazolidone; a tackifier; and a surfactant such as analkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid oraromatic carboxylic acid.

If necessary, a development accelerator can be added to the colordeveloper.

The development accelerators include thioether compounds described inJapanese Patent Publication for Opposition Purpose (hereinafter referredto as "J. P. KOKOKU") Nos. Sho 37-16088, 37-5987, 38-7826, 44-12380 and45-9019 and U.S. Pat. No. 3,813,247; p-phenylenediamine compoundsdescribed in J. P. KOKAI Nos. Sho 52-49829 and 50-15554; quaternaryammonium salts described in J. P. KOKAI No. Sho 50-137726, J. P. KOKOKUNo. Sho 44-30074 and J. P. KOKAI Nos. Sho 56-156826 and 52-43429; aminecompounds described in U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230,796and 3,253,919, J. P. KOKOKU No. Sho 41-11431 and U.S. Pat. Nos.2,482,546, 2,596,926 and 3,582,346; polyalkylene oxides described in J.P. KOKOKU Nos. Sho 37-16088 and 42-25201, U.S. Pat. No. 3,128,183, J. P.KOKOKU Nos. Sho 41-11431 and 42-23883 and U.S. Pat. No. 3,532,501; aswell as 1-phenyl-3-pyrazolidones and imidazoles. These developmentaccelerators are usable, if necessary.

When the color developer is used for processing a photosensitivematerial for photography, the replenisher is fed in an amount ofpreferably 550 ml or below, more preferably 450 ml of below, and mostpreferably 80 to 400 ml, per m². By reducing bromide ion concentrationin the replenisher or by using no bromide ion, the amount thereof can bereduced to 300 ml or below. In processing a photosensitive material forprints, the color developer replenisher is fed in an amount of 20 to 600ml, preferably 30 to 200 ml and more preferably 40 to 100 ml, per m² ofthe material.

In processing the photosensitive material for photography, theprocessing temperature with the color developer is preferably 35° C. orabove, more preferably 40° to 50° C. In processing the photosensitivematerial for prints, the processing temperature with the color developeris 20° to 50° C., preferably 30° to 45° C., and most preferably 37° to42° C.

In processing the photosensitive material for photography, theprocessing time with the color developer is preferably 30 seconds to 3minutes and 15 seconds, more preferably 30 seconds to 2 minutes and 30seconds. In processing the photosensitive material for printing, theprocessing time with the color developer is usually shorter than 3minutes, preferably 10 seconds to 1 minute and more preferably 10 to 30seconds. The term "processing time" (such as development time) hereinindicates the time necessitated from entering of the photosensitivematerial into a processing bath to entering of it into the nextprocessing bath.

It is preferred that the developer for the photosensitive material forprinting is substantially free from benzyl alcohol. To control thechange of the photographic characteristics during the continuous processand also to attain the effect of the present invention, it is alsopreferred that the developer for the photosensitive material forprinting is substantially free from sulfurous acid ion (the term"substantially free" herein indicates that sulfurous acid ionconcentration is not higher than 3.0×10⁻³ mol/l). Sulfurous acid ionconcentration is preferably not higher than 1.0×10⁻³ mol/l, and mostpreferably, the developer is free from sulfurous acid ion. It is to benoted, however, that a very small amount of sulfurous acid ion used,before the preparation of the developer, for inhibiting the oxidation ofthe processing agent kit containing a concentrated developing agent isnot included therein. To control the change of the photographicchracteristics depending on the change in concentration of ahydroxylamine, it is more preferred that the developer is substantiallyfree from the hydroxylamine (the term "substantially free" hereinindicates that the hydroxylamine concentration is not higher than5.0×10⁻³ mol/l). It is most preferred that the developer is completelyfree from the hydroxylamine.

It is preferred to inhibit the evaporation of the developer andoxidation thereof by air. The contact area of the processing liquid withair in the processing vessel can be represented by the opening ratedefined as follows:

    Opening rate= (contact area of processing solution with air (cm.sup.2)!/ volume of processing solution (cm.sup.3)!

The opening rate (cm⁻¹) defined as above is preferably not higher than0.05, more preferably in the range of 0.0005 to 0.01. The opening rateis reduced by covering the surface of the photographic processingsolution in the processing vessel with a floating lid or the like, byproviding a movable lid as described in J.P. KOKAI No. Hei 1-82033 or bya slit development process described in J.P. KOKAI No. Sho 63-216050. Itis preferred that the processing solution in a colordeveloper-replenishing tank or in a processing tank is sealed with ahigh-boiling organic solvent or a high-molecular compound to reduce thecontact area thereof with air. It is particulrly preferred to use liquidparaffin, an organosiloxane or the like. The opening rate can be reducednot only in the color development and black-and-white development stepsbut also in all of the subsequent steps such as bleaching,bleach-fixing, fixing, water washing and stabilization steps.

The developer can be reused by regeneration. The term "regeneration ofthe developer" herein indicates that the used developer is treated withan anion exchange resin or by electrodialysis and that the activity ofthe developer is increased by adding a processing agent called"regenerating agent". The regeneration rate (rate of the overflow in thereplenisher) is preferably at least 70%, particularly at least 90%.

The color-developed photosensitive material is then usually desilvered.The desilverization process herein basically comprises bleaching processand fixing process. Both processes can be conducted at the same time bya bleach-fixing process or these processes are combined with each other.

The bleaching agents include, for example, iron salts; compounds ofpolyvalent metals such as iron (III), cobalt (III), chromium (IV) andcopper (II); peracids; quinones; and nitro compounds. Typical bleachingagents are, for example, ferric chloride, ferricyanides, bichromates;organic complex salts of iron (III) (such as metal complex salts ofaminopolycarboxylic acids, e. g. ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycolether diaminetetraacetic acid); persulfates; bromates; permanganates;and nitrobenzenes. Among them, preferred are ferricaminopolycarboxylates and salts of them as described on page 11 of theabove-mentioned J. P. KOKAI No. Hei 3-144446. Examples of them includeferric salts of ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycolether diaminetetraacetic acid. Other bleaching agents include complexsalts of citric acid, tartaric acid and malic acid. Among them,particularly preferred are iron (III) complex salt ofethylenediaminetetraacetic acid and iron (III) complex salts ofaminopolycarboxylic acids such as iron (III) complex salt of1,3-diaminopropanetetraacetic acid. Such an iron (III) complex salt ofaminopolycarboxylic acid is particularly effective in both bleachingsolution and bleach-fixing solution.

The bleaching solution, bleach-fixing solution, pre-bleaching bath andpre-bleach-fixing bath may contain a bleaching accelerator, ifnecessary. Examples of the bleaching accelerators include compoundshaving a mercapto group or disulfido bond described in U.S. Pat. No.3,893,858, West German Patent No. 1,290,812, J.P. KOKAI No. Sho 53-95630and Research Disclosure No. 17129 (July, 1978); thiazolidine derivativesdescribed in J.P. KOKAI No. Sho 50-140129; thiourea derivativesdescribed in U.S. Pat. No. 3,706,561; iodides described in J.P. KOKAINo. Sho 58-16235; polyoxyethylene compounds described in West GermanPatent No. 2,748,430; polyamine compounds described in J. P. KOKOKU No.Sho 45-8836; and bromide ions. Among them, compounds having a mercaptogroup or disulfido group and also having a remarkable acceleratingeffect are preferred. Particularly preferred are compounds described inU.S. Pat. No. 3,893,858, West German Patent No. 1,290,812 and J. P.KOKAI No. Sho 53-95630. Further, compounds described in U.S. Pat. No.4,552,834 are also preferred. These bleach-accelerators may be addedalso to the photosensitive material. When a color photosensitivematerial for photography is to be bleach-fixed, these bleachingaccelerators are particularly effective.

The desilvering bath may contain rehalogenating agents, pH bufferingagents and other known additives as described on page 12 of J. P. KOKAINo. Hei 3-144446, in addition to the bleaching agent.

An organic acid is preferably incorporated into the bleaching solutionand bleach-fixing solution in order to prevent a bleach stain, inaddition to the above-described compounds. Particularly preferredorganic acids are those having an acid dissotiation constant (pKa) of 2to 6 such as acetic acid, propionic acid, hydroxyacetic acid, succinicacid, maleic acid, glutaric acid, fumaric acid, malonic acid and adipicacid. Particularly preferred are succinic, maleic and glutaric acids.

The pH of the bleaching solution and bleach-fixing solution is usually4.0 to 8.0. For conducting the process more rapidly, pH can be furtherlowered.

The fixing agents usable for the fixing solution or bleach-fixingsolution include, for example, thiosulfates, thiocyanates, thioethercompounds, thioureas and a large amount of iodides. Among them, thethiosulfates are commonly used and ammonium thiosulfate is most widelyusable. A combination of a thiosulfate with a thiocyanate, thioethercompound or thiourea is also preferred.

Examples of preferred preservatives for the fixing solution andbleach-fixing solution include sulfites, hydrogensulfites,carbonylhydrogensulfite adducts and sulfinic acid compounds described inEuropean Patent No. 294769 A. Further, it is preferred to add achelating agent such as an aminopolycarboxylic acid or organicphosphonic acid to the fixing solution or bleach-fixing solution inorder to stabilize it. Examples of preferred chelating agents include1-hydroxyethylidene-1,1-diphosphonic acid,ethylenediamine-N,N,N,N'-tetrakis(methylenephosphonic acid),nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acidand 1,2-propylenediaminetetraacetic acid. Among them,1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraaceticacid are particularly preferred.

It is preferred to incorporate 0.1 to 10 mol/l of a compound having apKa of 6.0 to 9.0 such as imidazole, 1-methylimidazole, 1-ethylimidazoleor 2-methylimidazole into the fixing solution or bleach-fixing solutionin order to adjust pH thereof.

The fixing solution and bleach-fixing solution can further containvarious fluorescent brightening agents, antifoaming agents, surfactants,polyvinylpyrrolidones, methanol, etc.

When a replenishing system is employed in the process, the quantity ofthe fixing solution or bleach-fixing solution to be replenished ispreferably 100 to 3,000 ml, more preferably 300 to 1800 ml, per m² ofthe photosensitive material. The bleach-fixing solution can bereplenished by using a bleach-fixing replenisher or, as described inJ.P. KOKAI No. Sho 61-143755 or Japanese Patent Application No. Hei2-216389, overflowing bleaching solution and fixing solution can beused.

The total processing time for the photosensitive material forphotography in the desilvering step comprising bleaching, bleach-fixingand fixing is preferably 30 seconds to 3 minutes, more preferably 45seconds to 2 minutes. The processing temperature is 30° to 60° C.,preferably 35° to 55° C.

In processing with a processing solution having a bleaching effect, itis particularly preferred to conduct aeration so as to keep thephotographic properties very stable. The aeration can be conducted by amethod known in the art, such as blowing of air into the solution havingthe bleaching effect or absorption of air with an ejector.

The processing solution having the bleaching effect is reusable byrecovering the overflow used in the process and adding the components toregulate the composition thereof. Such a regeneration is easy in thepresent invention. The details of the regeneration are described onpages 39 to 40 of Fuji Film Processing Manual, Fuji Color Negative Film,CN-16 Process (revised in August, 1990) published by Fuji Photo FilmCo., Ltd.

An automatic developing machine used for developing the photosensitivematerial of the present invention preferably has a means of transportingthe photosensitive material as described in J. P. KOKAI Nos. Sho60-191257, 60-191258 and 60-191259. As described in J. P. KOKAI No. Sho60-191257, such a transportation means remarkably reduces the amount ofthe processing solution brought from the preceding bath into asubsequent bath, so that the deterioration in the function of theprocessing solution can be remarkably prevented. Such a function isparticularly effective in reducing the processing time in each step andalso in reducing the amount of the replenisher.

The desilverization step is usually followed by a step of washing withwater. This washing step may be replaced with a stabilization step. Inthe stabilization, any of known methods described in J. P. KOKAI Nos.Sho 57-8543, 58-14834 and 60-220345 can be employed. Water washingstep/stabilization step in which a stabilizing bath containing adye-stabilizing agent and a surfactant is used as the final bath mayalso be employed.

The water for washing and the stabilizing bath can contain a softeningagent for hard water such as an inorganic phosphoric acid,polyaminocarboxylic acid or organic aminophosphonic acid.

The amount of water used in the washing step varies in a wide rangedepending on the properties of the photosensitive material (which dependon, for example, couplers used), temperature of water used for washing,number of the tanks (number of stages), replenishing method such ascounter flow or down-flow system and various other conditions.

The stabilizing solution contains a compound which stabilizes the colorimage, selected from among, for example, formalin, benzaldehydes such asm-hydroxybenzaldehyde, formaldehyde/bisulfurous acid adduct,hexamethylenetetramine and derivatives thereof, hexahydrotriazine andderivatives thereof, dimethylurea, N-methylol compounds such asN-methylolpyrazole, organic acids and pH buffering agents. The preferredamount of these compounds is 0.001 to 0.02 mol per liter of thestabilizing solution. The free formaldehyde concentration in thestabilizing solution is preferably as low as possible so as to preventformaldehyde gas from sublimation.

Various surfactants can be incorporated into washing water andstabilizing solution so as to prevent the formation of water spots inthe course of drying of the photosensitive material. Among them,preferred is an anionic surfactant, particularly an alkylphenol/ethyleneoxide adduct. The alkylphenols are particularly preferably octyl-,nonyl-, dodecyl- and dinonylphenols. The molar number of ethylene oxideto be added is particularly preferably 8 to 14. It is also preferred touse a silicon surfactant having a high antifoaming effect.

The washing water and stabilizing solution preferably contain achelating agent. Preferred chelating agents include aminopolycarboxylicacids such as ethylenediaminetetraacetic acid anddiethylenetriaminepentaacetic acid; organic phosphonic acids such as1-hydroxyethylidene-1,1-diphosphonic acid, N,N,N'-trimethylenephosphonicacid and diethylenetriamine-N,N,N',N'-tetramethylenephosphonic acid; andhydrolyzates of maleic anhydride polymers described in European PatentNo. 345,172A1.

Water treated with a reverse osmosis membrane is effectively used as thewashing and/or stabilizing solution.

Preferably, each processing solution is used at 10° to 50° C. Althoughthe standard temperature ranges from 33° to 38° C., it is also possibleto accelerate the process and thereby to reduce the process time at ahigher temperature or, on the contrary, to conduct the process at alower temperature so as to improve the image quality and stability ofthe processing solution.

Each solution is usable for processing two or more kinds ofphotosensitive materials. For example, a color negative film and a colorpaper are processed with the same solution to reduce the cost of theprocessing machine and to simplify the process. The processing solutionsare usable for processing various color photosensitive materials such ascolor negative films for movies, color reversal films for slides ortelevision, color papers, color positive films and color reversalpapers. They are suitable also for film units with a lens described inJ. P. KOKOKU No. Hei 2-32615 and Japanese Utility Model Publication forOpposition Purpose (hereinafter referred to as "J. UM. KOKOKU") No. Hei3-39784.

The photosensitive materials must have at least one photosensitive layeron a support. A typical example of the silver halide photosensitivematerial comprises at least one color-sensitive layer (comprising two ormore silver halide emulsion layers having substantially the same-colorsensitivity but different degree of sensitivity) formed on the support.The photosensitive layer is a unit photosensitive layer sensitive to anyof blue, green and red lights. In the photographic photosensitivematerials for multi-layered silver halide color photographs, thearrangement of the unit photosensitive layers is generally as follows: ared-sensitive layer, a green-sensitive layer and a blue-sensitive layerin this order from the support. However, the order of the arrangementmay be reversed or a photosensitive layer having a different colorsensitivity may be interposed between layers having the same colorsensitivity. A photoinsensitive layer can be provided between the silverhalide photosensitive layers or as the top layer or the bottom layer.The photoinsensitive layer may contain a coupler, DIR compound,color-mixing inhibitor, etc. The two or more silver halide emulsionlayers constituting the unit photosensitive layer have preferably astructure consisting of two layers, i.e. a high sensitivity emulsionlayer and a low sensitivity emulsion layer, as described in D. E. PatentNo. 1,121,470 or G. B. Patent No. 923,045. Usually the arrangement ofthe layers is such that the sensitivity thereof decreases graduallytoward the support. An emulsion layer having a low sensitivity may beformed away from the support and an emulsion layer having a highsensitivity may be formed close to the support as described in J. P.KOKAI Nos. Sho 57-112751, 62-200350, 62-206541 and 62-206543.

The arrangement can be as follows: a blue-sensitive layer/GH/RH/GL/RLtoward the support as described in J. P. KOKOKU No. Sho 55-34932, or ablue-sensitive layer/GL/RL/GH/RH toward the support as described in J.P. KOKAI Nos. Sho 56-25738 and 62-63936.

Another arrangement is that of three layers having sensitivitiesgradually lowered toward the support, i.e. a top layer (a silver halideemulsion layer having the highest sensitivity), middle layer (a silverhalide emulsion layer having a lower sensitivity) and bottom layer (asilver halide emulsion layer having a sensitivity lower than that of themiddle layer) as described in J. P. KOKOKU No. Sho 49-15495. Even insuch an arrangement comprising three layers having sensitivitiesdifferent from each other, layers sensitive to the same color mayfurther comprise an emulsion layer having a medium sensitivity/emulsionlayer having a high sensitivity/emulsion layer having a low sensitivityin the order toward the support as described in J. P. KOKAI No. Sho59-202464. In another example, the arrangement may be as follows:high-sensitivity emulsion layer/low sensitivity emulsion layer/mediumsensitivity emulsion layer or low sensitivity emulsion layer/mediumsensitivity emulsion layer/high sensitivity emulsion layer. When thephotosensitive material has four or more layers, the arrangement of themmay be varied as described above.

For improving the color reproducibility, it is preferred to form a donorlayer (CL) having an interlayer effect and a spectral sensitivitydistribution different from that of the main photosensitive layers suchas BL, GL and RL at a position adjacent to or close to the mainphotosensitive layers as described in U.S. Pat. Nos. 4,663,271,4,705,744 and 4,707,436 and J. P. KOKAI Nos. Sho 62-160448 and 63-89850.

In an ordinary photosensitive material (color photograhic paper) forprints, the grains in the silver halide emulsions are spectrallysensitized with blue-sensitive, green-sensitive and red-sensitivespectrally sensitized dyes in the above-described order of the colorlayers, and the support is coated with them in the above-describedorder. However, the order of the coating of them may be varied. Namely,from the viewpoint of the rapid processing, the top layer is preferablya photosensitive layer containing silver halide grains having thelargest average grain size; and from the viewpoint of the storabilityunder the irradiation with light, the bottom layer is preferably amagenta-coloring photosensitive layer.

The structure of the photosensitive layer and color hue may be free fromthe above-described conditions, and at least one infrared-sensitivesilver halide emulsion layer may be used.

The silver halides preferably used for the photograhic photosensitivematerials include silver bromoiodide, silver chloroiodide and silverchlorobromoiodide containing at most about 30 molar % of silver iodide.Silver bromoiodide and silver chlorobromoiodide containing about 2 to 10molar % of silver iodide are particularly preferred.

The silver halide grains in the photographic emulsion may be in aregular crystal form such as a cubic, octahedral or tetradecahedralform; an irregular crystal form such as spherical or plate form; or acomplex crystal form thereof. They include also those having a crystalfault such as a twin plate.

The silver halide grain diameter may range from about 0.2 μm or less toas large as that having a projection area diameter of about 10 μm. Theemulsion may be either a polydisperse emulsion or monodisperse emulsion.The monodispersion emulsion having a dispersion factor of 15% or below,preferably 10% or below is preferred.

The silver halide photographic emulsion can be prepared by processesdescribed in, for example, Research Disclosure (hereinafter referred toas "RD"), No. 17643 (December, 1978), pp. 22 to 23, "1. Emulsionpreparation and types"; RD No. 18716 (November, 1979), p. 648; and RDNo. 307105 (November, 1989), pp. 863 to 865.

Tabular grains having an aspect ratio of 3 or higher are also usable.The tabular grains can be easily prepared by processes described in, forexample, Gutoff, Photographic Science and Engineering, Vol. 14, pp. 248to 257 (1970); U.S. Pat. Nos. 4,434,226; and G. B. Patent No. 2,112,157.

The crystal structure of the grains in the above emulsion may beuniform; the grains may comprise an inside portion and an outsideportion which are composed of silver halides different from each other;or the structure may be a laminated one. Different silver halide grainscan be bonded together by an epitaxial bond or they can be bonded with acompound other than silver halides such as silver rhodanate or leadoxide. A mixture of grains having various crystal forms can also beused.

The emulsion may be of a surface-latent image type for forming a latentimage mainly on the surface thereof, of an internal latent image typefor forming a latent image in the grains or of such a type that a latentimage is formed both on the surface and in the grains. The emulsion mustbe a negative one. In the internal latent image type emulsions, acore/shell type internal latent image type emulsion described in J.P.KOKAI No. Sho 63-264740 may also be used. Processes for producing theemulsion are described in J.P. KOKAI No. Sho 59-133542. The thickness ofthe shells in the emulsion which varies depending on the developingprocess is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion to be used in the present invention isusually physically and chemically ripened and spectrally sensitized. Theadditives to be used in these steps are shown in RD Nos. 17643, 18716and 307105. The portions in which the additives are mentioned in thesethree Research Disclosures are summarized in a table given below.

The amount of silver to be applied to the photographic photosensitivematerial is preferably not larger than 6.0 g/m², most preferably notlarger than 4.5 g/m².

The silver halide grains in the photosensitive material for prints arepreferably silver chloride, silver chlorobromide or silverchlorobromoiodide grains comprising at least 95 molar % of silverchloride. Particularly, for the rapid process, substantially silveriodide-free silver chlorobromide or silver chloride can be preferablyused. The term "substantially silver iodide-free" herein indicates thatsilver iodide content is not higher than 1 molar %, preferably nothigher than 0.2 molar %. Further, in some cases, high-silver chloridegrains containing 0.01 to 3 molar % of silver iodide on the emulsionsurface as described in J. P. KOKAI No. Hei 3-84545 are preferably usedso as to improve the high-intensity sensitivity, spectral sensitivity orstorability of the photosensitive material. Although the halogencomposition of the emulsion may be the same or different among thegrains, the properties of all the grains can be easily made uniform byusing an emulsion of grains having a uniform halogen composition. As forthe halogen composition distribution in the silver halide grains in theemulsion, grains can be suitably selected from among those having aso-called homogeneous structure in which the composition in any part ofthe grain is uniform; those having a so-called laminated structure inwhich the halogen composition in the core of the silver halide grain isdifferent from that in the shell (one or more layers) surrounding thecore; and those having a structure which has a non-layer part having adifferent halogen composition in the core or on the surface (when such aion-layer part is on the surface of the grain, the structure is suchthat the different composition part is conjugated with the edge, corneror surface of the grain).

It is also effective to further increase the silver chloride content ofthe silver halide emulsion for the purpose of reducing the amount of thedeveloper replenisher. In such a case, an emulsion comprisingsubstantially pure silver chloride, i. e. an emulsion having a silverchloride content of 98 to 100 molar %, is also preferably used.

The average grain size (number-average diameter of a circle having anarea equal to that of the projected area of the grain) of the silverhalide grains contained in the silver halide emulsion is preferably 0.1to 2 μm.

As for the grain size distribution, the coefficient of variation(calculated by dividing the standard deviation of the grain sizedistribution by the average grain size) is not higher than 20%,desirably not higher than 15%, and more desirably not higher than 10%.Namely, the emulsion is so-called monodisperse emulsion. In order toobtain a wide latitude, this monodisperse emulsion is preferably blendedin the same layer or it is applied to form an interlayer.

The localized silver halide grain phase or its substrate may contain adifferent metal ion or complex ion thereof. Preferred are those selectedfrom among ions and complexes of metals of the Groups VIII and IIb inthe Periodic table, and lead ion and thallium ion. The localized phasemainly contains an ion or complex ion of a metal selected from amongiridium, rhodium and iron, and the substrate mainly contains an ion orcomplex ion of a metal selected from among osmium, iridium, rhodium,platinum, ruthenium, palladium, cobalt, nickel and iron. The kind andconcentration of the metal ion in the locallized phase may be differentfrom those in the substrate. A combination of two or more kinds of thesemetals can also be used. It is particularly preferred that the iron andiridium compounds are in the silver bromide locallized phase.

The silver halide emulsion is usually chemically and spectrallysensitized.

The chemical sensitization is conducted with a chalcogen sensitizer (inparticular, sulfur sensitization typified by the addition of an unstablesulfur compound, selenium sensitization with a selenium compound ortellurium sensitization with a tellurium compound). A noble metalsensitization typified by gold sensitization and reduction sensitizationcan be conducted either separately or in combination of them. Compoundspreferably used for the chemical sensitization are those described fromthe right lower column on page 18 to the right upper column on p. 22 ofJ. P. KOKAI No. Sho 62-215272.

The silver halide emulsion can contain various compounds or precursorsthereof so as to prevent the fogging during the production, storage orprocessing of the photosensitive material, or to stabilize thephotographic properties. Preferred examples of these compounds aredescribed on pages 39 to 72 of the above-mentioned J. P. KOKAI No. Sho62-215272. Further, 5-arylamino-1,2,3,4-thiatriazole compounds (the arylresidue has at least one electron-attractive group) described inEuropean Patent No. 0447647 are also preferably used.

The spectral sensitization is conducted for the purpose of imparting aspectral sensitivity in a desired wavelength range to the emulsion forforming each layer of the photosensitive material.

The spectral sensitizing dyes used for the spectral sensitization inblue, green and red zones include, for example, those described in F. M.Harmer, Heterocyclic compounds--Cyanine dyes and related compounds(published by John Wiley & Sons New York, London! in 1964). Examples ofthe preferred compounds and the spectral sensitization method aredescribed from the right upper column, page 22 to page 38 of theabove-mentioned J. P. KOKAI No. Sho 62-215272. As for the red-sensitivespectral sensitizing dyes for the silver halide grains having a highsilver chloride content, spectral sensitizing dyes described in J. P.KOKAI No. Hei 3-123340 are very excellent in the stability, adsorptionstrength and dependence of the exposure on the temperature.

For the efficient spectral sensitization of the infrared zone,sensitizing dyes described from the left upper column, page 12 to theleft lower column, page 21 of J. P. KOKAI No. Hei 3-15049; from the leftlower column, page 4 to the left lower column, page 15 of J. P. KOKAINo. Hei 3-20730; from line 21, page 4 to line 54, page 6 of EuropeanPatent No. 0,420,011; from line 12, page 4 to line 33, page 10 ofEuropean Patent No. 0,420,012; European Patent No. 0,443,466 and U.S.Pat. No. 4,975,362 are preferably used.

A dye (particularly oxonol or cyanine dye) which can be decolored by theprocess as described on pages 27 to 76 of European Patent No. 0,337,490A2 can be incorporated into the hydrophilic colloid layer for thepurpose of preventing the irradiation or halation or improving thesafety of the safelight.

Some of the water-soluble dyes impair the color separation or safety ofthe safelight when they are used in an increased amount. Preferred dyesusable without impairing the color separation are water-soluble dyesdescribed in Japanese Patent Application Nos. Hei 03-310143, 03-310189and 03-310139.

Gelatin is advantageously used as the binder or protective colloid forthe photosensitive materials. Other hydrophilic colloids can also beused either singly or in combination with gelatin. Preferred gelatin isa low-calcium gelatin having a calcium content of at most 800 ppm, morepreferably at most 200 ppm. An antifungal agent as described in J. P.KOKAI No. Sho 63-271247 is preferably used in order to prevent thepropagation of various fungi and bacteria in the hydrophilic colloidlayer, since they deteriorate the image.

In the printer exposure of the photosensitive material for printing, aband stop filter described in U.S. Pat. No. 4,880,726 is preferably usedfor eliminating the photo-color-mixing and also for remarkably improvingthe color reproducibility.

After the completion of the exposure, the photosensitive material can besubjected to an ordinary color development process. To rapidly conductthe process, it is preferred to conduct bleach-fixing after the colordevelopment. Particularly when the above-described high-silver chlorideemulsion is used, pH of the bleach-fixing solution is preferably nothigher than about 6.5, particularly not higher than about 6, foraccelerating the desilverization.

The photographic additives usable herein are also mentioned in RD, andthe corresponding portions are shown in the following table:

    ______________________________________                                        Additive   RD 17643   RD 18716    RD 307105                                   ______________________________________                                        1.  Chemical   p. 23      p. 648, right                                                                           p. 866                                        sensitizer            column                                              2.  Sensitivity           p. 648, right                                           improver              column                                              3.  Spectral   pp. 23 to 24                                                                             p. 648, right                                                                           pp. 866 to 868                                sensitizer and        colum to p. 649,                                        supersensitizer       right column                                        4.  Brightening                                                                              p. 24      p. 647, right                                                                           p. 868                                        agent                 column                                              5.  Light absorber,                                                                          pp. 25 to 26                                                                             p. 649, right                                                                           p. 873                                        filter, dye and       column to p. 650,                                       UV absorber           left column                                         6.  Binder     p. 26      p. 651, left                                                                            pp. 873 to 874                                                      column                                              7.  Plasticizer                                                                              p. 27      p. 650, right                                                                           p. 876                                        and lubricant         column                                              8.  Coating aid                                                                              pp. 26 and 27                                                                            p. 650, right                                                                           pp. 875 to 876                                and surfactant        column                                              9.  Antistatic p. 27      p. 650, right                                                                           pp. 876 to 877                                agent                 column                                              10. Matting agent                   pp. 878 to 879                            ______________________________________                                    

The photosensitive material can contain various dye-forming couplers.Among them, the following couplers are particularly preferred:

Yellow couplers: couplers represented by formulae (I) and (II) in EP502,424A; those of formulae (I) and (II) in E.P. No. 513,496A(particularly Y-28 on page 18); those of general formula (I) in claim 1of Japanese Patent Application No. Hei 4-134523; those of generalformula (I) in lines 45 to 55, column 1 of U.S. Pat. No. 5,066,576;those of general formula (I) in paragraph 0008 of J. P. KOKAI No. Hei4-274425; those set forth in claim 1 on p. 40 of E. P. No. 498,381A1particularly D-35 on p. 18); those of formula (Y) on p. 4 of E. P. No.447,969A1 (particularly Y-1 on p. 17 and Y-54 on p. 41); and those ofgeneral formulae (II) to (IV) in lines 36 to 58, column 7 of U.S. Pat.No. 4,476,219 (particularly II-17, 19 (column 17) and II-24 (column19)!,

Acylacetanilide couplers: particularly pivaloylacetanilide couplershaving a halogen atom or alkoxyl group at the o-position of the anilidering; acylacetanilide couplers wherein the acyl group is acycloalkanecarbonyl group having a substituent at the 1-position asdescribed in E. P. No. 0,447,969A and J. P. KOKAI Nos. Hei 5-107701 and5-113642; and malondianilide couplers described in E. P. Nos. 0,482,552Aand 0,524,540A,

Magenta couplers: those described in J. P. KOKAI No. Hei 3-39737 L-57(right lower column, p. 11), L-68 (right lower column, p. 12) and L-77(right lower column, p. 13); A-4!-63 (p. 134), A-4!-73 and 75 (p. 139)of E. P. No. 456,257; M-4 and 6 (p. 26) and M-7 (p. 27) of E. P. No.486,965; M-45 in paragraph 0024 of Japanese Patent Application No. Hei4-234120; M-1 in paragraph 0036 of Japanese Patent Application No. Hei4-36917; and M-22 in paragraph 0237 of J. P. KOKAI No. Hei 4-362631,

5-Pyrazolone magenta couplers: those of arylthio-linked coupling-offtype described in W.O. 92/18901, 92/18902 and 92/18903,

Pyrazoloazole couplers: those containing a sulfonamido group in themolecule as described in J. P. KOKAI No. Sho 61-65246; those having analkoxyphenylsulfonamido ballast group as described in J. P. KOKAI No.Sho 61-147254; and those having an alkoxy or aryloxy group at the6-position as described in EP Nos. 226,849A and 294,785A,

Cyan couplers: CX-1, 3, 4, 5, 11, 12, 14 and 15 (pp. 14 to 16) of J. P.KOKAI No. Hei 4-204843; C-7 and 10 (p. 35), 34 and 35 (p. 37),, (I-1)and (I-17) (pp. 42 to 43) of J. P. KOKAI No. Hei 4-43345; and those ofgeneral formula (Ia) or (Ib) in claim 1 of Japanese Patent ApplicationNo. Hei 4-236333,

Polymer couplers: P-l and P-5 (p. 11) of J. P. KOKAI No. Hei 2-44345,and

Phenol couplers and naphthol couplers; diphenylimidazole cyan couplersdescribed in J. P. KOKAI No. Hei 2-33144; 3-hydroxypyridine cyancouplers described in E. P. No. 0,333,185A2; cyclic active methylenecyan couplers described in J. P. KOKAI No. Sho 64-32260; pyrrolopyrazolecyan couplers described in E. P. No. 0,456,226A1; pyrroloimidazole cyancouplers described in E. P. No. 0,484,909; and pyrrolotriazole cyancouplers described in E. P. Nos. 0488,248 and 0,491,197A1.

The couplers capable of forming a colored dye having a suitablediffusibility are preferably those described in U.S. Pat. No. 4,366,237,G.B. Patent No. 2,125,570, E. P. No. 96,873B and DE P. No. 3,234,533.

The couplers used for compensation for unnecessary absorption of thecolored dye are preferably as follows: yellow-colored cyan couplers offormulae (CI), (CII), (CIII) and (CIV) on p. 5 of E. P. No. 456,257A1(particularly YC-86 on p. 84); yellow-colored magenta coupler ExM-7 (p.202), EX-1 (p. 249) and EX-7 (p. 251) described in E. P. No. 456,257A1;magenta-colored cyan coupler CC-9 (column 8) and CC-13 (column 10)described in U.S. Pat. No. 4,833,069; couplers (2) (column 8) in U.S.Pat. No. 4,837,136; and colorless masking couplers of formula (A) inclaim 1 of WO 92/11575 (particularly compounds given on pages 36 to 45).

Compounds (including couplers) capable of reacting with an oxidationproduct of the developing agent to form a photographically usefulcompound residue are as follows: development inhibitor-releasingcompounds such as compounds of formulae (I), (II), (III) and (IV) onpage 11 of E. P. No. 378,236A1 particularly compounds T-101 (p. 30),T-104 (p. 31), T-113 (p. 36), T-131 (p. 45), T-144 (p. 51) and T-158(p.58)!, compounds of formula (I) on page 7 of E. P. No. 436,938A2particularly D-49 (p. 51)!, compounds of formula (1) in Japanese PatentApplication No. Hei 4-134523 particularly (23) in paragraph 0027!,compounds of formulae (I), (II) and (III) on pages 5 to 6 of E. P. No.440,195A2 particularly I-(1) on page 29!; bleachingaccelerator-releasing compounds such as compounds of formulae (I) and(II) on page 5 of E. P. No. 310,125A2 particularly (60) and (61) on p.61! and compounds of formula (I) in claim 1 of Japanese PatentApplication No. Hei 4-325564 particularly (7) in paragraph 0022!;ligand-releasing compounds such as those of LIG-X in claim 1 of U.S.Pat. No. 4,555,478 (particularly compounds in lines 21 to 41 in column12); leuco dye-releasing compounds such as compounds 1 to 6 in columns 3to 8 of U.S. Pat. No. 4,749,641; fluorescent dye-releasing compoundssuch as compounds represented by COUP-DYE in claim 1 of U.S. Pat. No.4,774,181 (particularly compounds 1 to 11 in columns 7 to 10);development accelerator- or fogging agent-releasing compounds such asthose of formulae (1), (2) and (3) in column 3 of U.S. Pat. No.4,656,123 particularly (I-22) in column 25! and ExZK-2 in lines 36 to 38on page 75 of E. P. No. 450,637A2; compounds which do not release adye-forming group before coupling-off such as compounds of formula (I)in claim 1 of U.S. Pat. No. 4,857,447 (particularly Y-1 to Y-19 incolumns 25 to 36).

As additives other than the couplers, those described below arepreferred.

Dispersion medium for oil-soluble organic compounds: P-3, 5, 16, 19, 25,30; 42, 49, 54, 55, 66, 81, 85, 86 and 93 (pp. 140 to 144) described inJ. P. KOKAI No. Sho 62-215272; latices for impregnation of oil-solubleorganic compounds: latices described in U.S. Pat. No. 4,199,363;oxidized developing agent scavengers: compounds of formula (I) in lines54 to 62, column 2 of U.S. Pat. No. 4,978,606 particularly l-(1), (2),(6) and (12) in columns 4 and 5! and those of formulae in lines 5 to 10,column 2 of U.S. Pat. No. 4,923,787 particularly compound 1 (column 3)!;antistaining agents: those of formulae (I) to (III) in lines 30 to 33,p. 4 of E. P. No. 298,321A, particularly I-47, 72, III-i and 27 (pp. 24to 48); discoloration inhibitors: A-6, 7, 20, 21, 23, 24, 25, 26, 30,37, 40, 42, 48, 63, 90, 92, 94 and 164 of E. P. No. 298,321A (pp. 69 to118), II-1 to III-23 in columns 25 to 38 of U.S. Pat. No. 5,122,444,particularly III-10, I-1 to III-4 on pp. 8 to 12 of E. P. No. 471,347A,particularly II-2, and A-1 to 48 in columns 32 to 40 of U.S. Pat. No.5,139,931, particularly A-39 and 42; materials capable of reducing theamount of color image increasing agent or color mixing-inhibitor used:I-1 to II-15 on pp. 5 to 24 of E. P. No. 411,324A, particularly I-46;formalin scavengers: SCV-1 to 28 on pp. 24 to 29 of E. P. No. 477,932A,particularly SCV-8; hardeners: H-1, 4, 6, 8 and 14 on p. 17 of J. P.KOKAI No. Hei 1-214845, and compounds (H-1 to 54) of formulae (VII) to(XII) in columns 13 to 23 of U.S. Pat. No. 4,618,573, compounds (H-1 to76) of formula (6) in the right, lower part on p. 8 of J. P. KOKAI No.Hei 2-214852, particularly H-14, and compounds set forth in claim 1 ofU.S. Pat. No. 3,325,287; development inhibitor precursors: P-24, 37 and39 (pp. 6 and 7) of J. P. KOKAI No. Sho 62-168139; and compounds setforth in claim 1 of U.S. Pat. No. 5,019,492, particulrly 28 and 29 incolumn 7; antiseptics and mildew-proofing agents: I-1 to III-43 incolumns 3 to 15 of U.S. Pat. No. 4,923,790, particularly II-1, 9, 10, 18and III-25; stabilizers and antifoggants: I-1 to (14) in columns 6 to 16of U.S. Pat. No. 4,923,793, particularly I-1, 60, (2) and (13), andcompounds 1 to 65 in columns 25 to 32 of U.S. Pat. No. 4,952,483,particularly 36; chemical sensitizers: triphenylphosphine selenide andcompound 50 of J. P. KOKAI No. Hei 5-40324; dyes: a-l to b-20 on pp. 15to 18 of J. P. KOKAI No. Hei 3-156450, particularly a-1, 12, 18, 27, 35,36 and b-5, V-1 to 23 on pp. 27 to 29, particularly V-1, F-I-1 toF-II-43 on pp. 33 to 55 of E. P. No. 445,627A, particularly F-I-11 andF-II-8, III-1 to 36, on pp. 17 to 28 of E. P. No. 457,153A, particularlyIII-1 and 3, fine crystal dispersions of Dye-1 to 124 on pp. 8 to 26 ofW088/04794, compounds 1 to 22 on pp. 6 to 11 of E. P. No. 319,999A,particularly compound 1, compounds D-1 to 87 of formulae (1) to (3) (pp.3 to 28) of E. P. No. 519,306A, compounds 1 to 22 (columns 3 to 10) offormula (I) in U.S. Pat. No. 4,268,622, and compounds (1) to (31) offormula (I) (columns 2 to 9) of U.S. Pat. No. 4,923,788; and UVabsorbers: compounds (18b) to (18r) of formula (1) and 101 to 427 (pp. 6to 9) of J. P. KOKAI No. 46-3335, compounds (3) to (66) (pp. 10 to 44)of formula (I), compounds HBT-1 to 10 (p. 14) of formula (III) of E. P.No. 520,938A, and compounds (1) to (31) of formula (1) (columns 2 to 9)of E. P. No. 521,823A.

The support used for the photosensitive material for printing may bemade of any material such as a glass, paper or plastic film so far asthe photographic emulsion layer can be applied thereto. The mostpreferred is a support of reflection type.

The term "support of reflection type" herein indicates a support havinga high reflectivity so as to obtain a clear dye image in the silverhalide emulsion layer. The supports of this type include those coatedwith a hydrophobic resin containing a light-reflecting substance such astitanium oxide, zinc oxide, calcium carbonate or calcium sulfatedispersed therein, and those comprising the hydrophobic resin per secontaining the light-reflecting substance dispersed therein. Thesupports include, for example, a polyethylene-coated paper, polyethyleneterephthalate-coated paper, synthetic polypropylene paper, transparentsupport having a reflective layer or containing a reflective substance,such as a glass plate, a polyester film such as polyethyleneterephthalate, cellulose triacetate or cellulose nitrate film, polyamidefilm, polycarbonate film, polystyrene film and vinyl chloride resinfilm. The preferred supports of reflection type used in the presentinvention are paper supports the both surfaces of which are each coatedwith a water-resistant resin layer, wherein at least one of thewater-resistant resin layers contains fine white pigment particles.

The water-resistant resins used for forming the reflective support arethose having a water absorption of not higher than 0.5% by weight,preferably not higher than 0.1% by weight. They include polyolefins suchas polyethylene, polypropylene and other ethylene polymers; vinylpolymers and copolymers thereof such as polystyrene, polyacrylate andcopolymers of them; and polyesters such as polyethylene terephthalateand polyethylene isophthalate and copolymers thereof. Particularlypreferred are polyethylene and polyesters.

The polyethylenes usable herein are high-density polyethylene,low-density polyethylene, linear low-density polyethylene and blends ofthese polyethylenes. These polyethylene resins preferably have a meltflow rate (hereinafter referred to as "MFR") in the range of 1.2 to 12g/10 min as determined under conditions 4 in Table 1 of JIS K 7210before processing. The term "MFR of polyolefin resin before processing"herein indicates MFR of the resin before blending it with a blueingagent or white pigment.

The supports suitable for the photosensitive material are described, forexample, on page 28 of the above-described RD. 17643; from right column,page 647 to left column, page 648 of RD. 18716; and on page 879 of RD307105.

The photosensitive material for the photography has a total thickness ofthe hydrophilic colloidal layers on the emulsion layer-side of 23 μm orbelow, preferably 20 μm or below, and particularly 13 to 17 μm. Thefilm-swelling rate T_(1/2) is preferably 5 to 15 seconds T_(1/2) isdefined to be the time necessitated for attaining the thickness of ahalf (1/2) of the saturated film thickness when 90% of the maximumswelled film thickness in defined as the saturated film thickness, themaximum swelled film thickness being obtained by processing with a colordeveloping solution at 30° C. for 3 minutes and 15 seconds. Thefilm-swelling rate T_(1/2) can be controlled by adding a hardener togelatin used as the binder or by varying the time conditions after thecoating. The swelling rate is preferably 150 to 350%. The swelling ratecan be calculated from the maximum thickness of the swollen filmobtained under the above-described conditions by the following formula:

     (Maximum thickness of swollen film)-(film thickness)!/(film thickness).

The photosensitive material can have a hydrophilic colloid layer (inother words, back layer) having a total thickness of 2 to 20 μm on drybasis on the opposite side to the emulsion layer. The back layerpreferably contains the above-described light absorber, filter dye,ultraviolet absorber, antistatic agent, hardener, binder, plasticizer,lubricant, coating aid, surfactant, etc. The swelling rate of the backlayer is preferably 150 to 500%.

The photosensitive materials preferably used in the present inventionare those described below.

The photosensitive materials preferably used herein are those having amagnetic recording layer which comprises magnetic particles (preferablyferromagnetic iron oxide particles coated with Co, and the like)dispersed in a binder. The recording layer is preferably opticallytransparent and covers the whole surface of the photosensitive material.The magnetic particles may be treated with a coupling agent as describedin J. P. KOKAI No. Hei 6-161032. Polymers described in, for example, J.P. KOKAI No. Hei 4-219569 are preferably used as the binder. Althoughthe recording layer may be formed in any part of the support, it ispreferably formed on the opposite side (back layer) of the support tothe emulsion layer. Preferably, a layer containing a lubricant is formedon the recording layer and a matting agent is contained in the outmostphotosensitive emulsion layer on the support.

The photosensitive material preferably contains an antistatic agent sothat it still has the antistatic properties even after the developmentprocess. Preferred antistatic agents are electroconductive metal oxidesand ionic polymers. The antistatic agent is preferably used so as toobtain an electric resistance of not above 10¹² Ω.cm at a temperature of25° C. and RH of 10%.

The photosensitive materials having the magnetic recording layer aredescribed in U.S. Pat. Nos. 5,336,589, 5,250,404, 5,229,259 and5,215,874 and EP 466,130A.

The support for the photosensitive material is preferably a thin layerof a polyester having no rolling properties. The thickness of thesupport is 50 to 105 μm, and the main material therefor is preferably apolyethylene aromatic dicarboxylate polyester (particularly a polyesterproduced mainly from benzenedicarboxylic acid or naphthalenedicarboxylicacid and ethylene glycol). The support has a glass transitiontemperature of preferably 50° to 200° C. The surface of the support isprocessed by ultraviolet irradiation, corona discharge, glow dischargeor flaming. The support is preferably heat-treated at a temperature inthe range of 40° C. to the glass transition temperature of the supportfor 0.1 to 1,500 hours before or after the formation of the subbinglayer and before the formation of the emulsion layer. The support aswell as photosensitive material, development process and cartridge aredescribed in Kokai Giho (public disclosure) No. 94-6023 published byHatsumei Kyokai (Japan Institute of Invention and Innovation) in 1994!.

EXAMPLES

The following Examples will further illustrate the present invention,which by no means limit the invention.

Example 1

Compound (D-2) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR12## Synthesis ofcompound (3):

23.8 g of the compound (1), 15.0 g of sodium iodide, 34.0 g of sodiumhydrogencarbonate and 70 ml of N,N-dimethylacetamide were fed into athree-necked flask. 37.8 ml of the compound (2) was dropped into theobtained mixture under stirring and heating to an outer temperature of130° C. for a period of 10 minutes. After the completion of the droppingfollowed by heating and stirring for 3 hours, the reaction mixture wascooled to room temperature. 400 ml of ethyl acetate and 400 ml of waterwere added to the mixture and then the obtained mixture was stirred toconduct the extraction. The ethyl acetate layer thus obtained was washedwith a mixture of 300 ml of water and 100 ml of saturated aqueous commonsalt solution 4 times, and then dried over anhydrous sodium sulfate. Theproduct was concentrated with a rotary evaporator. The residue waspurified by silica gel column chromatography to obtain 29.4 g (yield:58.5%) of the intended compound (3).

Synthesis of compound (5):

28.4 g of 2,5-dichloroaniline and 300 ml of water were fed into athree-necked flask, and 59.3 ml of sulfuric acid was added to theresultant mixture under stirring under cooling with ice. A solution of13.4 g of sodium nitrite in 25 ml of water was dropped into the obtainedmixture for a period of 10 minutes while the inner temperature was keptat 8° C. or below. After the completion of the dropping, the stirringwas continued for 30 minutes. Separately, 29.4 g of the compound (3), 96g of sodium acetate, 67 ml of acetic acid and 200 ml of methanol werefed into another three-necked flask, and the diazonium salt solutionprepared as described above was added thereto under stirring and coolingwith ice while the inner temperature was kept at 16° C. or below. Inthis step, the reaction procedure was followed by TLC, and the additionof the diazonium salt solution was stopped when the compound (3) haddisappeared from the reaction system. After the completion of theaddition followed by stirring for 30 minutes, methanol was distilled offunder reduced pressure. The reaction mixture was poured into ice andneutralized by adding a sodium hydroxide solution, and then 1.5 l ofethyl acetate and 500 ml of water were added thereto to conduct theextraction. The obtained ethyl acetate layer was washed with a mixtureof 700 ml of water and 200 ml of saturated aqueous common salt solutionfour times and then dried over anhydrous sodium sulfate. The product wasconcentrated with a rotary evaporator and the obtained residue waspurified by silica gel column chromatography to obtain 25.5 g of theintended compound (5) (yield: 51%).

Synthesis of compound (D-2):

25.5 g of the compound (5), 2 g of palladium-carbon (10%) and 73 ml ofmethanol were fed into an autoclave and stirred at room temperatureunder a hydrogen pressure of 100 atm for 5 hours. A solution of 21.6 gof naphthalene-1,5-disulfonic acid tetrahydrate in 40 ml of methanol wasadded to the obtained reaction mixture. The resultant mixture wasfiltered and the filtrate was concentrated with a rotary evaporator. 200ml of ethyl acetate and 200 ml of water were added to the concentrate,and the resultant mixture was stirred to obtain a solution, therebyforming layers. The aqueous layer was separated and washed with 200 mlof ethyl acetate three times. The aqueous layer thus obtained wasconcentrated with a rotary evaporator. Crystals separated from thesolution in mixed methanol and ethanol were taken by filtration toobtain 22.2 g (yield: 67%) of the intended compound (D-2).

NMR(D₂ O): δ=8.82 (d, 2H, J=9.7 Hz), 8.20 (d, 2H, J=9.7 Hz), 7.73 (dd,2H, J=9.7 Hz, 9.7 Hz), 7.28 (m, 1H), 7.2 to 7.4 (m, 2H), 3.80 (t, 2H,J=8.3 Hz), 3.4-3.7 (m, 15H), 3.10 (t, 2H, J=8.3 Hz).

Example 2

Compound (D-40) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR13## Synthesis ofcompound (8):

135 g of aniline, 365.4 g of sodium hydrogencarbonate and 500 ml ofN,N-dimethylacetamide were fed into a three-necked flask. 140 g of thecompound (7) was dropped into the obtained mixture under stirring andheating to an outer temperature of 120° C. for a period of 30 minutes.After the completion of the dropping followed by heating at an outertemperature of 130° C. and stirring for 3 hours, the reaction mixturewas cooled to room temperature. 1 l of ethyl acetate and 600 ml of waterwere added to the mixture and the extraction was conducted. The ethylacetate layer thus obtained was washed with a mixture of 600 ml of waterand 200 ml of saturated aqueous common salt solution 3 times, and thendried over anhydrous sodium sulfate. The product was concentrated with arotary evaporator. The residue was purified by silica gel columnchromatography to obtain 82 g (yield: 35%) of the intended compound (8).

Synthesis of compound (9):

140 g of the compound (8), 420 ml of xylene and 355.7 g of zinc (II)chloride were fed into a three-necked flask, and the obtained mixturewas stirred under heating and reflux for 5 hours and then cooled to roomtemperature. An aqueous solution of 1.5 l of hexane and 626.4 g ofsodium hydroxide in 900 ml of water was added to the reaction mixture,and the obtained mixture was stirred and then filtered by suction withCelite. The hexane layer of the obtained filtrate was concentrated witha rotary evaporator. The residue was purified by silica gel columnchromatography to obtain 70.1 g (yield: 50%) of the intended compound(9).

Synthesis of compound (10):

10.0 g of the compound (9), 5.5 g of sodium iodide, 15.6 g of sodiumhydrogencarbonate and 30 ml of N,N-dimethylacetamide were fed into athree-necked flask, and 9.3 ml of 2-(2-chloroethoxy)ethanol was droppedthereinto under stirring and heating at an outer temperature of 130° C.for a period of 10 minutes. After the completion of the dropping, theheating and stirring were continued for additional 3 hours and then thereaction mixture was cooled to room temperature. 200 ml of ethyl acetateand 200 ml of water were added thereto and the obtained mixture wasstirred. After the extraction, the obtained ethyl acetate layer waswashed with a mixed solution of 150 ml of water and 50 ml of saturatedaqueous common salt solution four times and then dried over anhydroussodium sulfate. The product thus obtained was concentrated with a rotaryevaporator, and the residue was purified by silica gel columnchromatography to obtain 10.0 g (yield: 64.5%) of the intended compound(10).

Synthesis of compound (11):

10.0 g of the compound (10), 39.4 g of sodium acetate, 27.4 ml of aceticacid and 30 ml of methanol were fed into a three-necked flask. The samediazonium salt solution as that obtained in the same manner as that inthe synthesis of the compound (5) was added thereto under stirring andcooling with ice to keep the inner temperature not higher than 16° C. Inthis step, the reaction procedure was traced by TLC, and the addition ofthe diazonium salt solution was stopped when the compound (10) haddisappeared in the reaction system. After the completion of the additionfollowed by stirring for 30 minutes, methanol was distilled off underreduced pressure. The reaction mixture was poured into ice andneutralized by adding a sodium hydroxide solution, and then 300 ml ofethyl acetate and 300 ml of water were added thereto to conduct theextraction. The obtained ethyl acetate layer was washed with a mixtureof 200 ml of water and 100 ml of saturated aqueous common salt solutionfour times and then dried over anhydrous sodium sulfate. The product wasconcentrated with a rotary evaporator and the obtained residue waspurified by silica gel column chromatography to obtain 9.5 g (yield:56%) of the intended compound (11).

Synthesis of compound (D-40):

10.0 g of the compound (11), 0.5 g of palladium-carbon (10%) and 100 mlof methanol were fed into an autoclave and stirred at room temperatureunder a hydrogen pressure of 100 atm for 5 hours. A solution of 8.6 g ofnaphthalene-1,5-disulfonic acid tetrahydrate in 20 ml of methanol wasadded to the obtained reaction mixture. The resultant mixture wasfiltered and the filtrate was concentrated with a rotary evaporator. 200ml of ethyl acetate and 200 ml of water were added to the concentrate,and the resultant mixture was stirred to obtain a solution, therebyforming layers. The aqueous layer was separated and washed with 200 mlof ethyl acetate three times. The aqueous layer thus obtained wasconcentrated with a rotary evaporator. Crystals separated from thesolution in mixed methanol and ethanol were taken by filtration toobtain 10.0 g (yield: 75%) of the intended compound (D-40).

NMR(D₂ O): δ=8.86 (d, 2H, J=9.3 Hz), 8.21 (d, 2H, J=9.3 Hz), 7.72 (dd,2H, J=9.3 Hz, 9.3 Hz), 7.47 (s, 1H), 7.32 (s, 2H), 2.8-3.9 (m, 10H), 1.9to 2.1 (m, 1H), 1.7 to 1.9 (m, 1H), 1.42 (s, 3H), 1.28 (d, 3H, J=8.3Hz), 1.16 (s, 3H).

Example 3

Compound (D-46) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR14## Synthesis ofcompound (13):

105.1 g of the compound (12), 200 ml of acetonitrile and 80 ml ofN,N-dimethylacetamide were fed into a three-necked flask. 80.5 ml ofthionyl chloride was dropped into the obtained mixture under stirringand cooling to an inner temperature of 12° C. or below. After thecompletion of the dropping followed by stirring for 1 hour, 93.1 g ofaniline was dropped while the inner temperature was kept at 20° C. orbelow. After continuing the stirring for additional 10 minutes, 162 mlof pyridine was dropped while the inner temperature was kept at 18° C.or below. After continuing the stirring for additional 30 minutes, 1 lof water was added thereto, and the obtained mixture was stirred. Thecrystals thus formed were filtered by suction to obtain 161 g (yield:92%) of the intended compound (13).

Synthesis of compound (14):

160 g of the compound (13) and 450 ml of methylene chloride were fedinto a three-necked flask and then 266.6 g of aluminum (III) chloridewas added thereto while keeping the inner temperature below 20° C. bycooling with ice. After the completion of the addition, the ice bath wastaken out, the reaction mixture was stirred for 3 hours and then pouredinto ice/water. After extraction with 2 l of ethyl acetate, the obtainedethyl acetate layer was washed with a mixed solution of 800 ml of waterand 200 ml of saturated aqueous common salt solution three times andthen dried over anhydrous sodium sulfate. After the concentration with arotary evaporator, 350 ml of acetonitrile was added to the residue, andthe crystals thus obtained were filtered by suction to obtain 108 g(yield: 68%) of the intended compound (14).

Synthesis of compound (15):

25 g of lithium aluminum hydride and 400 ml of tetrahydrofuran were fedinto a three-necked flask. A solution of 87.6 g of the compound (14) and200 ml of tetrahydrofuran was dropped thereinto at such a rate thattetrahydrofuran was refluxed at a moderate speed under stirring. Afterthe completion of the dropping, the stirring was continued under heatingand reflux for additional one hour. 100 ml of ethyl acetate and then 100ml of methanol were dropped thereinto. 1 l of ethyl acetate and 500 mlof water were added thereto and then a solution of 120 g of sodiumhydroxide in 500 ml of water was added thereto. The reaction mixture wasfiltered by suction with Celite. Ethyl acetate layer separated from thefiltrate was washed with a mixed solution of 400 ml of water and 100 mlof saturated aqueous common salt solution three times. The product wasconcentrated with a rotary evaporator to obtain the intended compound(15) as the crude product, which was then sent to the next step withoutpurification.

Synthesis of compound (17):

20.0 g of the compound (15), 11.2 g of sodium iodide, 31.2 g of sodiumhydrogencarbonate and 65 ml of N,N-dimethylacetamide were fed into athree-necked flask, and 52.3 g of the compound (16) (synthesized fromtetraethylene glycol and p-toluenesulfonyl chloride) was droppedthereinto under stirring and heating at an outer temperature of 80° C.for a period of 1 hour. After the completion of the dropping, theheating and stirring were continued for additional 5 hours and then thereaction mixture was cooled to room temperature. 500 ml of ethyl acetateand 500 ml of water were added thereto. After the extraction, theobtained ethyl acetate layer was washed with a mixed solution of 400 mlof water and 100 ml of saturated aqueous common salt solution four timesand then dried over anhydrous sodium sulfate. The product thus obtainedwas concentrated with a rotary evaporator, and the residue was purifiedby silica gel column chromatography to obtain 39.4 g (yield: 94%) of theintended compound (17).

Synthesis of compound (18):

39.0 g of the compound (17), 114 g of sodium acetate, 79 ml of aceticacid and 140 ml of methanol were fed into a three-necked flask. The samediazonium salt solution as that obtained in the same manner as that inthe synthesis of the compound (5) was added thereto under stirring andcooling with ice to keep the inner temperature not higher than 14° C. Inthis step, the reaction procedure was traced by TLC, and the addition ofthe diazonium salt solution was stopped when the compound (17) haddisappeared from the reaction system. After the completion of theaddition followed by stirring for 30 minutes, methanol was distilled offunder reduced pressure. The reaction mixture was poured into ice andneutralized by adding a sodium hydroxide solution, and then 800 ml ofethyl acetate and 700 ml of water were added thereto to conduct theextraction. The obtained ethyl acetate layer was washed with a mixtureof 400 ml of water and 100 ml of saturated aqueous common salt solutionfour times and then dried over anhydrous sodium sulfate. The product wasconcentrated with a rotary evaporator and the obtained residue waspurified by silica gel column chromatography to obtain 30.0 g (yield:51%) of the intended compound (18).

Synthesis of compound (D-46):

30.0 of the compound (18), 1.5 g of palladium-carbon (10%) and 250 ml ofmethanol were fed into an autoclave and stirred at room temperatureunder a hydrogen pressure of 100 atm for 5 hours. A solution of 21.2 gof naphthalene-1,5-disulfonic acid tetrahydrate in 50 ml of methanol wasadded to the obtained reaction mixture. The resultant mixture wasfiltered and the filtrate was concentrated with a rotary evaporator. 200ml of ethyl acetate and 200 ml of water were added to the concentrate,and the resultant mixture was stirred to obtain a solution, therebyforming layers. The aqueous layer was separated and washed with 200 mlof ethyl acetate three times. The aqueous layer thus obtained wasconcentrated with a rotary evaporator to obtain 35.5 g (yield: 94%) ofthe intended compound (D-46).

NMR(D₂ O): δ=8.83 (d, 2H, J=9.3 Hz), 8.20 (d, 2H, J=9.3 Hz), 7.71 (dd,2H, J=9.3 Hz, 9.3 Hz), 7.49 (s, 1H), 7.28 (s, 2H), 3.4-3.8 (m, 21H), 1.9to 2.1 (m, 1H), 1.22 (s, 6H).

Example 4

Compound (D-48) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR15## Synthesis ofcompound (19):

232.8 g of aniline and 7.6 g of iodine were fed into a three-neckedflask. 734 ml of acetone was dropped into the resultant mixture understirring and under heating to an outer temperature of 200° C. for aperiod of 6 hours. Low-boiling components such as water formed in thereaction system were collected in a cooling device fixed on a branchpipe and distilled off. After the completion of the dropping, theobtained reaction mixture was distilled to obtain 142 g (yield: 33 g) ofthe intended compound (19).

b.p.: 138° to 142° C./16 mmHg.

Synthesis of compound (20):

142 g of the compound (19), 10 g of palladium-carbon (10%) and 450 ml ofethanol were fed into an autoclave and stirred at room temperature undera hydrogen pressure of 100 atm for 5 hours. After the completion of thestirring followed by the filtration, the filtrate was concentrated witha rotary evaporator to obtain 144 g of the intended compound (20) as thecrude product, which was then sent to the next step withoutpurification.

Synthesis of compound (21)

70.1 g of the compound (20), 60.0 g of sodium iodide, 134.4 g of sodiumhydrogencarbonate and 250 ml of N,N-dimethylacetamide were fed into athree-necked flask. 278.9 g of the compound (16) (synthesized fromtetraethylene glycol and p-toluenesulfonyl chloride) was droppedthereinto for a period of 1 hour. After the completion of the droppingfollowed by heating and stirring for additional 5 hours, the reactionmixture was cooled to room temperature. 1 l of ethyl acetate and 1 l ofwater were added to the reaction mixture to conduct the extraction. Theobtained ethyl acetate layer was washed with a mixed solution of 800 mlof water and 200 ml of saturated aqueous common salt solution fourtimes, and then dried over anhydrous sodium sulfate. The product wasconcentrated with a rotary evaporator and the obtained residue waspurified by silica gel column chromatography to obtain 64.7 g (yield:46%) of the intended compound (21).

Synthesis of compound (22):

36.7 g of the compound (21), 85 g of sodium acetate and 59 ml of aceticacid were fed into a three-necked flask. The same diazonium saltsolution as that obtained in the same manner as that in the synthesis ofthe compound (5) was added thereto under stirring and cooling with iceto keep the inner temperature not higher than 15° C. In this step, thereaction procedure was traced by TLC, and the addition of the diazoniumsalt solution was stopped when the compound (22) had disappeared fromthe reaction system. After the completion of the addition followed bystirring for 30 minutes, methanol was distilled off under reducedpressure. The reaction mixture was poured into ice and neutralized byadding a sodium hydroxide solution, and then 2 l of ethyl acetate and 1l of water were added thereto to conduct the extraction. The obtainedethyl acetate layer was washed with a mixture of 800 ml of water and 200ml of saturated aqueous common salt solution four times and then driedover anhydrous sodium sulfate. The product was concentrated with arotary evaporator and the obtained residue was purified by silica gelcolumn chromatography to obtain 25.8 g (yield: 47%) of the intendedcompound (22).

Synthesis of the compound (D-48):

25.8 g of the compound (22), 2 g of palladium-carbon (10%) and 73 ml ofmethanol were fed into an autoclave and stirred at room temperatureunder a hydrogen pressure of 100 atm for 3 hours. A solution of 17.7 gof naphthalene-1,5-disulfonic acid tetrahydrate in 40 ml of methanol wasadded to the obtained reaction mixture. The resultant mixture wasfiltered and the filtrate was concentrated with a rotary evaporator. 200ml of ethyl acetate and 200 ml of water were added to the concentrate toobtain a solution which formed layers. The aqueous layer was separatedand washed with 200 ml of ethyl acetate three times. The aqueous layerthus obtained was concentrated with a rotary evaporator to obtain 20.9 g(yield: 65%) of the intended compound (D-48).

NMR(D₂ O): δ=8.86 (d, 2H, J=9.7 Hz), 8.21 (d, 2H, J=9.7 Hz), 7.72 (dd,2H, J=9.7 Hz, 9.7 Hz), 7.50 (d, 2H, J=13.8 Hz), 7.38 (s, 1H), 2.8-3.8(m, 20H), 1.7 to 2.1 (m, 2H), 1.30 (s, 3H), 1.22 (d, 3H, J=9.7 Hz), 1.12(s, 3H).

Example 5

Compound (D-91) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR16## Synthesis ofcompound (24):

The compound (24) was obtained from 3-isopropylaniine in the same manneras that in the synthesis of the compound (19).

b. p.: 160° to 165° C./12 mmHg.

Synthesis of compound (25):

The compound (25) was obtained from compound (24) in the same manner asthat in the synthesis of the compound (20).

Synthesis of compound (26):

26.1 g of the compound (25), 18.0 g of sodium iodide, 30.2 g of sodiumhydrogencarbonate and 75 ml of N,N-dimethylacetamide were fed into athree-necked flask, and 62.7 g of the compound (16) was dropped into theresultant mixture under stirring and heating at an outer temperature of130° C. for a period of 1 hour. after continuing the stirring andheating for additional 5 hours, 31.4 g of the compound (16) was droppedthereinto for a period of 1 hour. After the completion of the droppingfollowed by stirring under heating for 3 hours, the reaction mixture wascooled to room temperature. 700 ml of ethyl acetate and 500 ml of waterwere added thereto to conduct the extraction. The obtained ethyl acetatelayer was washed with a mixed solution of 400 ml of water and 100 ml ofsaturated aqueous common salt solution, and then dried over anhydroussodium sulfate. The product thus obtained was concentrated with a rotaryevaporator, and the residue was purified by silica gel columnchromatography to obtain 30.4 g (yield: 64%).

Synthesis of compound (27):

30.4 g of the compound (26), 63 g of sodium acetate, 44 ml of aceticacid and 400 ml of methanol were fed into a three-necked flask. The samediazonium salt solution as that obtained in the same manner as that inthe synthesis of the compound (5) was added thereto under stirring andcooling with ice to keep the inner temperature not higher than 15° C.After confirming that the compound (26) had disappeared by TLC, theaddition of the diazonium salt solution was stopped, and the stirringwas continued for additional 30 minutes. Methanol was distilled offunder reduced pressure. The reaction mixture was poured into ice andneutralized by adding a sodium hydroxide solution, and then 1.5 l ofethyl acetate and 1 l of water were added thereto to conduct theextraction. The obtained ethyl acetate layer was washed with a mixtureof 800 ml of water and 200 ml of saturated aqueous common salt solutionfour times and then dried over anhydrous sodium sulfate. The product wasconcentrated with a rotary evaporator and the obtained residue waspurified by silica gel column chromatography to obtain 30.0 g (yield:68%) of the intended compound (27).

Synthesis of compound (D-91):

30.0 g of the compound (27), 3 g of palladium-carbon (10%) and 70 ml ofmethanol were fed into an autoclave and stirred at room temperatureunder a hydrogen pressure of 100 atm for 7 hours. A solution of 19.1 gof naphthalene-1,5-disulfonic acid tetrahydrate in 40 ml of methanol wasadded to the obtained reaction mixture. The resultant mixture wasfiltered and the filtrate was concentrated with a rotary evaporator. 200ml of ethyl acetate and 200 ml of water were added to the concentrate toobtain a solution. The aqueous layer thus obtained was separated andthen washed with 200 ml of ethyl acetate three times. The aqueous layerthus obtained was concentrated with a rotary evaporator to obtain 35.1 g(yield: 95%) of the intended compound (D-91).

NMR(D₂ O): δ=8.88 (d, 2H, J=9.7 Hz), 8.21 (D, 2H, J=9.7 Hz), 7.72 (dd,2H, J=9.7 Hz, 9.7 Hz), 7.34 (s, 1H), 7.28 (s, 1H), 2.7 to 3.8 (m, 21H),1.7 to 2.1 (m, 2H), 1.45 (s, 3H), 1.1 to 1.3 (m, 12H).

Example 6

Compound (D-86) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR17## Synthesis ofcompound (24):

472 ml of acetic anhydride was fed into a three-necked flask. 270.4 g ofthe compound (23) was dropped thereinto under refluxing and heating withstirring for a period of 30 minutes. After the completion of thedropping followed by stirring under heating and refluxing for 3 hours,90 ml of water was dropped thereinto for a period of 15 minutes. Thereaction mixture was cooled to an inner temperature of 30° C. 1 l ofethyl acetate and 1 l of water were added to the mixture and theextraction was conducted. The ethyl acetate layer thus obtained waswashed with a mixture of 800 ml of water and 200 ml of saturated aqueouscommon salt solution 3 times, and then dried over anhydrous sodiumsulfate. The product was concentrated with a rotary evaporator to obtain390 g of the intended compound (24) as the crude product, which was thensent to the next step without purification.

Synthesis of compound (25):

1 l of N,N-dimethylacetamide was added to the compound (24) to dissolvethe compound. 246.9 g of potassium-t-butoxy was added thereto at theroom temperature followed by stirring for 1 hour. The mixture was cooledto the inner temperature of -5° C. in ice-methanol bath. 247.9 ml ofprenyl chloride was dropped thereinto under stirring for a period of 1hour. The inner temperature was raised to 7° C. After the completion ofthe dropping followed by stirring for additional 2 hours, 2 l of ethylacetate and 1.5 l of water were added to the mixture and the extractionwas conducted. The ethyl acetate layer thus obtained was washed with amixture of 1 1 of water and 200 ml of saturated aqueous common saltsolution 4 times, and then dried over anhydrous sodium sulfate. Theproduct was concentrated with a rotary evaporator to obtain the intendedcompound (25) as the crude product, which was then sent to the next stepwithout purification.

Synthesis of compound (26):

1.2 l of ethanol was added to the compound (25) to dissolve thecompound. A solution of 320 g of sodium hydroxide in 320 ml of water wasdropped thereinto for a period of 20 minutes under heating andrefluxing. The reaction mixture was refluxed for additional 3 hoursunder heating. Another solution of 320 g of sodium hydroxide in 320 mlof water was dropped thereinto for a period of 20 minutes. The mixturewas refluxed again under heating for additional 3 hours. A solution of160 g of sodium hydroxide in 160 ml of water was dropped thereinto for aperiod of 5 minutes. After the mixture was refluxed under heating andstirring, the solvent was distilled off under the reduced pressure, 1544ml of the concentrated hydrochloric acid was dropped thereinto coolingwith ice for a period of 1 hour. The inner temperature was raised to 30°C. 1.5 l of ethyl acetate was added to the mixture and the extractionwas conducted. The ethyl acetate layer thus obtained was washed with amixture of 1 l of water and 200 ml of saturated aqueous common saltsolution 4 times, and then dried over anhydrous sodium sulfate. Theproduct was concentrated with a rotary evaporator and the obtainedresidue was purified by silica gel column chromatography to obtain 305.7g (yield: 75%) of the intended compound (26) as oil.

Synthesis of compound (27):

305.7 g of the compound (26) and 500 ml of xylene were fed into athree-necked flask. 613 g of zinc (II) chloride was added thereto withstirring and then the mixture was refluxed under heating and stirringfor 3 hours. The reaction mixture was cooled to the temperature of 70°C. 1.5 l of ethyl acetate and 1.5 l of water were added to the mixtureand the extraction was conducted. The ethyl acetate layer thus obtainedwas washed with a solution of 80 g of sodium hydroxide in 1 l of water 3times, then washed again with a mixture of 200 ml of saturated aqueouscommon salt solution and 800 ml of water 3 times. The ethyl acetatelayer was dried over anhydrous sodium sulfate. The product wasconcentrated with a rotary evaporator and the obtained residue waspurified by silica gel column chromatography to obtain 174.2 g (yield:57%) of the intended compound (27) as oil.

Synthesis of compound (28):

87.1 g of the compound (27), 288 g of sodium bicarbonate, 64.2 g ofsodium iodide and 200 ml of N,N-dimethylacetamide were fed into athree-necked flask. The mixture was stirred at the inner temperature of120° C. under heating. 145 g of the compound (2) was dropped thereintofor a period of 1 hour. After the completion of the dropping, theheating and stirring were continued for additional 13 hours at 130° C.and then the reaction mixture was cooled to 30° C. 600 ml of ethylacetate and 500 ml of water were added thereto and the extraction wasconducted. The thus-obtained ethyl acetate layer was washed with a mixedsolution of 100 ml of saturated aqueous common salt solution and 400 mlof water four times and then dried over anhydrous sodium sulfate. Theproduct thus obtained was concentrated with a rotary evaporator, and theresidue was purified by silica gel column chromatography to obtain 84.6g (yield: 59%) of the intended compound (28) as oil.

Synthesis of compound (29):

249 g of 2-(2-chloroethoxy) ethanol, 3.8 g of p-toluenesulfonic acidmonohydrate and 590 ml of dichloromethane were fed into a three-neckedflask. 500 ml of dihydropyran was dropped thereinto for a period of 30minute at room temperature with stirring. The temperature of thereaction system was raised as the dropping, and then the mixture reachedreflux state. After the completion of the dropping, the stirring wascontinued for additional 3 hours and then 10 g of sodium bicarbonate wasadded thereto followed by stirring for additional 10 minutes. Thereaction mixture was poured into a mixture of 100 g of sodiumbicarbonate and ice-water. 590 ml of dichloromethane added thereto andthe extraction was conducted. The thus-obtained dichloromethane layerwas washed with a mixed solution of 100 ml of saturated aqueous commonsalt solution and 400 ml of water four times and then dried overanhydrous sodium sulfate. 4 g of sodium hydroxide was added thereto andthe product thus obtained was concentrated with a rotary evaporator. Theresidue was distilled to collect the fraction of from 88° C. to 100°C./0.2 mmHg to obtain 350 g (yield: 84%) of the intended compound (29).

Synthesis of compound (30):

84.1 g of the compound (28), 14.06 g of sodium hydroxide and 200 ml oftoluene were fed into a three-necked flask. 131 g of the compound (29)was dropped thereinto under refluxing and heating with stirring for aperiod of 2 hours. After the completion of the dropping followed bystirring under heating and refluxing for additional 30 minutes, toluenewas distilled off under the reduced pressure. 500 ml of dichloromethaneand 300 ml of water were added thereto to dissolve them. 250 ml ofconcentrated hydrochloric acid was added thereto with stirring to makethe mixture acidic and then the mixture was neutralized by adding sodiumbicarbonate thereto. The dichloromethane layer obtained by theextraction of the mixture was washed with a mixed solution of 100 ml ofsaturated aqueous common salt solution and 400 ml of water 3 times andthen dried over anhydrous sodium sulfate. The product thus obtained wasconcentrated with a rotary evaporator to obtain the intended compound(30) as the crude product, which was then sent to the next step withoutpurification.

Synthesis of compound (31):

500 ml of methanol was added to the compound (30) to dissolve thecompound. 21.5 ml of the concentrated hydrochloric acid was droppedthereinto and then stirred for 1 hour. The solvent was distilled offunder the reduced pressure, 500 ml of ethyl acetate and 300 ml of waterwere added thereto and then the mixture was neutralized by adding sodiumbicarbonate thereto. The ethyl acetate layer obtained by the extractionof the mixture was washed with a mixed solution of 50 ml of saturatedaqueous common salt solution and 300 ml of water 4 times and then driedover anhydrous sodium sulfate. The product thus obtained wasconcentrated with a rotary evaporator. The residue was purified bysilica gel column chromatography to obtain 84.7 g (yield: 80%) of theintended compound (31) as oil.

Synthesis of compound (32):

84.7 g of the compound (31), 56.6 ml of the concentrated hydrochloricacid and 400 ml of methanol were fed into a three-necked flask. Aaqueous solution of 19.3 g of sodium nitrite in 20 ml of water wasdropped thereinto under stirring for a period of 15 minutes cooling withice. After the stirring for additional 5 hours without the ice bath, thereaction mixture was mixed with 100 g of sodium bicarbonate. 500 ml ofethyl acetate and 300 ml of water were added to the mixture and theextraction was conducted. The ethyl acetate layer thus obtained waswashed with a mixed solution of 50 ml of saturated aqueous common saltsolution and 150 ml of water 3 times and then dried over anhydroussodium sulfate. The product thus obtained was concentrated with a rotaryevaporator. The residue was purified by silica gel column chromatographyto obtain 44.6 g (yield: 49%) of the intended compound (32) as oil.

Synthesis of compound (D-86):

44.6 g of the compound (32), 5 g of the palladium-carbon (10%) and 100ml of methanol were fed into an autoclave and stirred at roomtemperature under a hydrogen pressure of 100 atm for 3 hours. A solutionof 35.5 g of naphthalene-1,5-disulfonic acid tetrahydrate in 90 ml ofmethanol was added to the obtained reaction mixture. The resultantmixture was filtered and the filtrate was stirred to precipitate acrystal. 58.5 g of the intended compound (D-86) was obtained (yield:82%).

NMR(D₂ O) δ=8.86 (d, 2H, J=9.7 Hz), 8.21 (d, 2H, J=9.7 Hz), 7.72 (dd,2H, J=9.7 Hz 9.7 Hz), 7.22 (s, 1H), 3.0-3.9 (m, 23H), 2.80 (t, 2H, J=8.0Hz), 1.95 (t, 2H, J=8.0 Hz), 1.30 (s, 6H), 1.21 (d, 6H, J=8.4 Hz).

Example 7

Compound (D-70) of the present invention shown above was synthesizedaccording to the following reaction scheme: ##STR18## Synthesis ofcompound (34):

The intended compound (34) was obtained by the same manner as that inthe synthesis of the compound (19) as a starting material ofm-toluidine: m.p., 152°-156° C./15 mmHg.

Synthesis of compound (35):

416.9 g of the compound (34), 1.2 l of N,N-dimethylacetamide were fedinto a three-necked flask. 190 ml of acetyl chloride was dropped intothe thus-obtained mixture under stirring and cooling with ice for aperiod of 30 minutes. After 216 ml of pyridine was dropped substantiallyfor a period of 1 hour, the reaction mixture was stirred for additional3 hours without a ice bath. 2 l of ethyl acetate and 2 l of water wereadded to the mixture and the extraction was conducted. The ethyl acetatelayer thus obtained was washed with a mixed solution of 500 ml ofsaturated aqueous common salt solution and 1.5 l of water 4 times andthen dried over anhydrous sodium sulfate. The product thus obtained wasconcentrated with a rotary evaporator. The residue was purified bysilica gel column chromatography to obtain 462 g (yield: 90%) of theintended compound (34) as oil.

Synthesis of compound (36):

462 g of the compound (34) and 1.5 l dichloromethane were fed into athree-necked flask. 393.5 g of N-bromosuccinimide was dropped into thethus-obtained mixture under stirring cooling with ice for a period of 1hour maintaining the inner temperature of 15° C. or below. After thecompletion of the dropping followed by stirring for additional 1 hour, 1l of water was added to the mixture and the extraction was conducted.The dichloromethane layer thus obtained was washed with a mixed solutionof 500 ml of saturated aqueous common salt solution and 1 l of water 4times and then dried over anhydrous sodium sulfate. The product thusobtained was concentrated with a rotary evaporator. 1 l of acetonitrilewas added to the resulting residue followed by stirring, and subjectingthe precipitated crystals to filtration under reduced pressure to obtain347.5 g (yield: 56%) of the intended compound (36).

Synthesis of compound (37):

308.25 g of the compound (36), 600 ml of N,N-dimethylacetamide and 246 gof sodium acetate were fed into a three-necked flask, and thethus-obtained mixture was stirred under heating and refluxing for 2hours and then cooled to 30° C. 1.25 l of water was dropped into thereaction mixture, and the thus-obtained crystals were taken byfiltration under reduced pressure. After 400 ml of acetonitrile wasadded to the crystals followed by dissolution under stirring, thencooling with water, the crystals precipitated were taken by filtrationunder reduced pressure to obtain 244.3 g (yield: 85%) of the intendedcompound (37).

Synthesis of compound (38):

244.3 g of the compound (37) and 250 ml of tetrahydrofuran were fed intoa three-necked flask to dissolve the compound, and 1 l of ethanol wasadded thereto. A solution of 136 g of sodium hydoxide in 150 ml of waterwas then added to the mixture under stirring. After substantial stirringfor 1 hour, the solvent was distilled off under the reduced pressure.The reaction mixture was made to acidic by adding 292 ml of theconcentrated hydrochloric acid, and then 800 ml of ethyl acetate and 400ml of water was added thereto and stirred. The mixture was neutralizedby adding sodium bicarbonate thereto. The ethyl acetate layer obtainedby the extraction of the mixture was washed with a mixed solution of 100ml of saturated aqueous common salt solution and 400 ml of water 4 timesand then dried over anhydrous sodium sulfate. The product thus obtainedwas concentrated with a rotary evaporator to obtain the intendedcompound (38) as the crude product, which was then sent to the next stepwithout purification.

Synthesis of compound (39):

The compound (38), 20 g of the palladium-carbon (10%) and 400 ml ofethanol were fed into an autoclave and stirred at the inner temperatureof 50°-60° C. under a hydrogen pressure of 100 atm for 5 hours. Thereaction mixture was filtered and the filtrate was concentrated with arotary evaporator to obtain the intended compound (39) as the crudeproduct, which was then sent to the next step without purification.

Synthesis of compound (40):

The compound (39) and 500 ml of ethanol were fed into a three-neckedflask. 146 ml of the concentrated hydrochloric acid was added theretounder stirring and then the mixture was refluxed under heating andstirring. 96 ml of sulfuric acid was dropped thereinto for a period of10 minutes followed by refluxing under the heating and stirring foradditional 1 hour. The reaction mixture was cooled to 30° C. and thenmixed with 1 kg of sodium bicarbonate to neutralise it. 1 l of ethylacetate and 1 l of water was added thereto and the extraction wasconducted. The thus-obtained ethyl acetate layer was washed with a mixedsolution of 200 ml of saturated aqueous common salt solution and 800 mlof water four times and then dried over anhydrous sodium sulfate. Theproduct thus obtained was concentrated with a rotary evaporator. Ethylacetate and n-hexane were added to the residue and the thus-obtainedcrystals were subjected to filtration under reduced pressure to obtain125.7 g (yield: 72%) of the intended compound (40).

Synthesis of compound (41):

58.0 g of the compound (40), 70.6 g of sodium bicarbonate, 25.5 g ofsodium iodide and 100 ml of N,N-dimethylacetamide were fed into athree-necked flask. The mixture was stirred at the outer temperature of130° C. under heating. 42.4 g of 2-(2-chloroethoxy) ethanol was droppedthereinto for a period of 20 minutes. After the completion of thedropping, the mixture was refluxed under heating and stirring foradditional 5 hours. The reaction mixture was cooled to 30° C. withwater. 500 ml of ethyl acetate and 400 ml of water were added theretoand the extraction was conducted. The thus-obtained ethyl acetate layerwas washed with a mixed solution of 100 ml of saturated aqueous commonsalt solution and 300 ml of water four times and then dried overanhydrous sodium sulfate. The product thus obtained was concentratedwith a rotary evaporator, and the residue was purified by silica gelcolumn chromatography to obtain 41.6 g (yield: 51%) of the intendedcompound (41).

Synthesis of compound (42):

41.0 g of the compound (41), 40.4 ml of the concentrated hydrochloricacid and 80 ml of methanol were fed into a three-necked flask. Asolution of 13.8 g of sodium nitrite in 28 ml of water was droppedthereinto for a period of 15 minutes under stirring and cooling withice. The mixture was stirred for additional 5 hours without cooling, andthen mixed with 50 g of sodium bicarbonate. 500 ml of ethyl acetate and300 ml of water were added thereto and the extraction was conducted. Thethus-obtained ethyl acetate layer was washed with a mixed solution of 50ml of saturated aqueous common salt solution and 150 ml of water 3 timesand then dried over anhydrous sodium sulfate. The product thus obtainedwas concentrated with a rotary evaporator, and the residue was purifiedby silica gel column chromatography to obtain 38.0 g (yield: 84%) of theintended compound (42) as oil.

Synthesis of compound (D-70):

19.0 g of the compound (42), 0.5 g of the palladium-carbon (10%) and 100ml of methanol were fed into an autoclave and stirred at roomtemperature under a hydrogen pressure of 100 atm for 3 hours. A solutionof 21.6 g of naphthalene-1,5-disulfonic acid tetrahydrate in 45 ml ofmethanol was added to the thus-obtained reaction mixture. The resultantmixture was filtered and the filtrate was stirred to precipitate acrystal. 31.5 g of the intended compound (D-70) was obtained (yield:90%).

NMR(D₂ O): δ=8.86 (d, 2H, J=9.7 Hz), 8.21 (d, 2H, J=9.7 Hz), 7.72 (dd,2H, J=9.7 Hz, 9.7 Hz), 7.45 (s, 1H), 7.24 (s, 1H), 3.2-4.0 (m, 14H),2.8-3.1 (m, 1H), 2.36 (s, 3H), 1.8-2.3 (m, 2H), 1.50 (s, 3H), 1.10 (s,3H).

Example 8

Preparation of multi-layer color photosensitive material:

A multilayer color photosensitive material, which will be referred to as"sample 101", was prepared by forming layers of the followingcompositions:

(Compositions of photosensitive layers)

Main materials to be used for forming the layers are classified asfollows:

ExC: cyan coupler

ExM: magenta coupler

ExY: yellow coupler

ExS: sensitizing dye

UV: ultraviolet absorber

HBS: high-boiling organic solvent

H: gelatin hardener

The numerals for the respective components indicate the amount ofcoating given by g/m². Those for silver halides are given in terms ofsilver. Those for sensitizing dyes are given in terms of molar unit permol of the silver halide contained in the same layer.

(Sample 101)

The first layer (antihalation layer):

    ______________________________________                                        Black colloidal silver                                                                          silver    0.18                                              Glatin                      1.60                                              ExM-1                       0.11                                              ExF-1                       3.4 × 10.sup.-3                             ExF-2 (solid dispersed dye) 0.03                                              ExF-3 (solid dispersed dye) 0.04                                              HBS-1                       0.16                                              ______________________________________                                    

The second layer (intermediate layer):

    ______________________________________                                        ExC-2                  0.055                                                  UV-1                   0.011                                                  UV-2                   0.030                                                  UV-3                   0.053                                                  HBS-1                  0.05                                                   HBS-2                  0.02                                                   Polyethyl acrylate latex                                                                             8.1 × 10.sup.-2                                  Gelatin                1.75                                                   ______________________________________                                    

The third layer (low-speed red-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion A                                                                    silver    0.46                                             ExS-1                        5.0 × 10.sup.-4                            ExS-2                        1.8 × 10.sup.-5                            ExS-3                        5.0 × 10.sup.-4                            ExC-1                        0.16                                             ExC-3                        0.045                                            ExC-5                        0.0050                                           ExC-7                        0.001                                            ExC-8                        0.010                                            Cpd-2                        0.005                                            HBS-1                        0.090                                            Gelatin                      0.87                                             ______________________________________                                    

The fourth layer (medium-speed red-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion D                                                                    silver    0.70                                             ExS-1                        3.0 × 10.sup.-4                            ExS-2                        1.2 × 10.sup.-5                            ExS-3                        4.0 × 10.sup.-4                            ExC-1                        0.22                                             ExC-2                        0.055                                            ExC-5                        0.007                                            ExC-8                        0.009                                            Cpd-2                        0.036                                            HBS-1                        0.11                                             Gelatin                      0.70                                             ______________________________________                                    

The fifth layer (high-speed red-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion E                                                                    silver    1.62                                             ExS-1                        2.0 × 10.sup.-4                            ExS-2                        1.0 × 10.sup.-5                            ExS-3                        3.0 × 10.sup.-4                            ExC-1                        0.133                                            ExC-3                        0.040                                            ExC-6                        0.040                                            ExC-8                        0.014                                            Cpd-2                        0.050                                            HBS-1                        0.22                                             HBS-2                        0.10                                             Gelatin                      0.85                                             ______________________________________                                    

The sixth layer (intermediate layer)

    ______________________________________                                        Cpd-1              0.07                                                       HBS-1              0.04                                                       Polyethyl acrylate latex                                                                         0.19                                                       Gelatin            2.30                                                       ______________________________________                                    

The seventh layer (low-speed green-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion A                                                                    silver    0.24                                             Silver bromoiodide emulsion B                                                                    silver    0.10                                             Silver bromoiodide emulsion C                                                                    silver    0.14                                             ExS-4                        4.0 × 10.sup.-5                            ExS-5                        1.8 × 10.sup.-4                            ExS-6                        6.5 × 10.sup.-4                            ExM-1                        0.005                                            ExM-2                        0.30                                             ExM-3                        0.09                                             ExY-1                        0.015                                            HBS-1                        0.26                                             HBS-3                        0.006                                            Gelatin                      0.80                                             ______________________________________                                    

The eighth layer (medium-speed green-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion D                                                                    silver    0.94                                             ExS-4                        2.0 × 10.sup.-5                            ExS-5                        1.4 × 10.sup.-4                            ExS-6                        5.4 × 10.sup.-4                            ExM-2                        0.16                                             ExM-3                        0.045                                            ExY-1                        0.008                                            ExY-5                        0.030                                            HBS-1                        0.14                                             HBS-3                        8.0 × 10.sup.-3                            Gelatin                      0.90                                             ______________________________________                                    

The ninth layer (high-speed green-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion E                                                                    silver    1.29                                             ExS-4                        3.7 × 10.sup.-5                            ExS-5                        8.1 × 10.sup.-5                            ExS-6                        3.2 × 10.sup.-4                            ExC-4                        0.011                                            ExM-1                        0.016                                            ExM-4                        0.046                                            ExM-5                        0.023                                            Cpd-3                        0.050                                            HBS-1                        0.20                                             HBS-2                        0.08                                             Polyethyl acrylate latex     0.26                                             Gelatin                      0.82                                             ______________________________________                                    

The tenth layer (yellow filter layer)

    ______________________________________                                        Yellow colloidal silver                                                                          silver    0.010                                            Cpd-1                        0.10                                             ExF-5 (solid dispersed dye)  0.06                                             ExF-6 (solid dispersed dye)  0.06                                             ExF-7 (oil-soluble dye)      0.005                                            HBS-1                        0.055                                            Gelatin                      0.70                                             ______________________________________                                    

The eleventh layer (low-speed blue-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion A                                                                    silver    0.25                                             Silver bromoiodide emulsion C                                                                    silver    0.25                                             Silver bromoiodide emulsion D                                                                    silver    0.10                                             ExS-7                        8.0 × 10.sup.-4                            ExY-1                        0.010                                            ExY-2                        0.70                                             ExY-3                        0.055                                            ExY-4                        0.006                                            ExY-6                        0.075                                            ExC-7                        0.040                                            HBS-1                        0.25                                             Gelatin                      1.60                                             ______________________________________                                    

The twelfth layer (high-speed blue-sensitive emulsion layer)

    ______________________________________                                        Silver bromoiodide emulsion F                                                                    silver    1.30                                             ExS-7                        3.0 × 10.sup.-4                            ExY-2                        0.15                                             ExY-3                        0.06                                             HBS-1                        0.070                                            Gelatin                      1.13                                             ______________________________________                                    

The thirteenth layer (the first protective layer)

    ______________________________________                                                UV-2  0.08                                                                    UV-3  0.11                                                                    UV-4  0.26                                                                    HBS-1 0.09                                                                    Gelatin                                                                             1.20                                                            ______________________________________                                    

The fourteenth layer (the second protective layer)

    ______________________________________                                        Silver bromoiodide emulsion G                                                                    silver    0.10                                             H-1                          0.30                                             B-1 (diameter: 1.7 μm)    5.0 × 10.sup.-2                            B-2 (diameter: 1.7 μm)    0.10                                             B-3                          0.10                                             S-1                          0.20                                             Gelatin                      1.75                                             ______________________________________                                    

Further, the respective layers suitably contain W-1 to W-3, B-4 to B-6,F-1 to F-17, iron salts, lead salts, gold salts, platinum salts, iridiumsalts, palladium salts and rhodium salts in order to improve thestorability, processability, pressure resistance, mildew-proofing andbacteria-proofing properties, antistatic properties and coatingeasiness.

                  TABLE 1                                                         ______________________________________                                                               Coeffi-                                                                       cient of                                                                             Rate of                                               Average Average  variation                                                                            grains having                                         AgI     grain    of grain                                                                             diameter/thick-                                                                        Grain                                  Emul- content diameter diameter                                                                             ness ratio of                                                                          structure/                             sion  (%)     (μm)  (%)    at least 2 (%)                                                                         shape                                  ______________________________________                                        A     2.1     0.55     25     81       homo-                                                                         geneous                                                                       structure,                                                                    tabular                                B     9.1     0.63     26     84       triple                                                                        structure,                                                                    tabular                                C     3.1     0.60     24     98       triple                                                                        structure,                                                                    tabular                                D     4.2     0.80     19     92       triple                                                                        structure,                                                                    tabular                                E     3.2     1.10     17     96       triple                                                                        structure,                                                                    tabular                                F     10.8    1.75     27     60       double                                                                        structure,                                                                    tabular                                G     1       0.07     15      0       homo-                                                                         geneous                                                                       structure,                                                                    cubic                                  ______________________________________                                    

In Table 1:

(1) The emulsions A to F were reduction-sensitized with thiourea dioxideand thiosulfonic acid in the step of preparation of the grains asdescribed in an Example of J.P. KOKAI No. Hei 2-191938.

(2) The emulsions A to F were sensitized by gold sensitization, sulfursensitization and selenium sensitization methods in the presence of aspectral sensitizing dye mentioned above for each photosensitive layerand sodium thiocyanate as described in an Example of J.P. KOKAI No. Hei3-237450.

(3) In the preparation of tabular grains, a low-molecular weight gelatinwas used as described in an Example of J.P. KOKAI No. Hei 1-158426.

(4) Dislocation lines as described in J.P. KOKAI No. Hei 3-237450 wereobserved on the tabular grains with a high-voltage electron microscope.

Preparation of dispersion of organic solid disperse dye:

ExF-2 which will be described below was dispersed as follows: 21.7 ml ofwater, 3 ml of 5% aqueous solution of sodiump-octylphenoxyethoxyethanesulfonate and 0.5 g of 5% aqueous solution ofp-octylphenoxy polyoxyethylene ether (degree of polymerization: 10) werefed into a 700 ml pot mill. 5.0 g of dye ExF-2 and 500 ml of zirconiumoxide beads (diameter: 1 mm) were added thereto, and the mixture wasmilled with a BO type vibration ball mill (a product of Chuo Koki) for 2hours to obtain a dispersion. Then the dispersion was taken out andadded to 8 g of 12.5% aqueous gelatin solution. The beads were removedby filtration to obtain a dispersion of the dye in gelatin. The averagegrain diameter of the fine dye grains was 0.44 μm.

A solid dispersion of each of ExF-3, ExF-4 and ExF-6 was obtained in thesame manner as that described above. The average grain diameters of thefine dye grains were 0.24 μm, 0.45 μm and 0.52 μm, respectively. ExF-5was dispersed by a microprecipitation dispersion method described inExample 1 in E. P. No. 0,549,489 A. The average grain diameter was 0.06μm. ##STR19##

    ______________________________________                                        (Processing step)                                                                         Process Process  Amount of                                                                             Capacity of                              Step        time    temp.    replenisher*                                                                          tank, l                                  ______________________________________                                        Color development                                                                          3 min  40.0° C.                                                                        200 ml  2.0                                      Bleaching   30 sec  45.0° C.                                                                        130 ml  0.7                                      Fixing (1)  30 sec  45.0° C.                                                                        100 ml  0.7                                      Fixing (2)  30 sec  45.0° C.                                                                         70 ml  0.7                                      Washing with water                                                                        15 sec  45.0° C.                                                                        --      0.4                                      (1)                                                                           Washing with water                                                                        15 sec  45.0° C.                                                                        400 ml  0.4                                      (2)                                                                           Stabilization                                                                             15 sec  45.0° C.                                                                        400 ml  0.4                                      Drying      20 sec  80° C.                                             ______________________________________                                         *The amount of the replenisher is given per m.sup.2 of the photosensitive     material.                                                                     (The steps ranging from the washing with water (2) to the fixing (2) were     conducted with three tanks by countercurrent multistage cascade method.)      (The steps ranging from the fixing (2) to fixing (1) were conducted with      two tanks by countercurrent multistage cascade method.)                  

The description will be made on the composition of each solution:

    ______________________________________                                                             Mother                                                   (Color developer)    liquid    Replenisher                                    ______________________________________                                        Diethylenediaminetetraacetic acid                                                                  4.0    g      4.0  g                                     Sodium 4,5-dihydroxybenzene-1,3-                                                                   0.5    g      0.5  g                                     disulfonate                                                                   Sodium sulfite       3.9    g      6.5  g                                     Potassium carbonate  37.5   g      39.0 g                                     Potassium bromide    2.7    g      --                                         Potassium iodide     1.3    mg     --                                         N-Methylhydroxylamine hydrochloride                                                                4.5    g      5.5  g                                     2-Methyl-4- N-ethyl-N-(β-hydroxyethyl)                                                        5.0    g      9.0  g                                     amino!-aniline sulfate (P-5)                                                  Water ad             1000   ml     1000 ml                                    pH (adjusted with potassium hydroxide                                                              10.05         10.25                                      and sulfuric acid)                                                            ______________________________________                                                             Mother                                                   (Bleaching solution) liquid    Replenisher                                    ______________________________________                                        Ferric ammonium 1,3-diaminopropanetetra-                                                           0.33   mol    0.50 mol                                   acetate monohydrate                                                           Ferric nitrate nonahydrate                                                                         0.30   mol    4.5  mol                                   Ammonium bromide     0.80   mol    1.20 mol                                   Ammonium nitrate     0.20   mol    0.30 mol                                   Acetic acid          0.67   mol    1.0  mol                                   Water ad             1000   ml     1000 ml                                    pH (adjusted with ammonia water)                                                                   4.5           4.0                                        ______________________________________                                        (Fixing solution) (common to the mother liquid and replenisher)               ______________________________________                                        (g)                                                                           Ammonium sulfite       28                                                     Aqueous ammonium thiosulfate solution (700 g/l)                                                      280       ml                                           Imidazole              15                                                     Ethylenediaminetetraacetic acid                                                                      15                                                     Water                  1.0       l                                            pH (adjusted with ammonia water and                                                                  5.8                                                    acetic acid)                                                                  ______________________________________                                    

(Washing water) (common to the mother liquid and replenisher)

Tap water was passed through a mixed bed column packed with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B; a product ofRohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400;a product of Rohm & Haas Co.) to reduce calcium and magnesium ionconcentration to 3 mg/l or below, and then 20 mg/l of sodiumisocyanurate dichloride and 0.15 g/l of sodium sulfate were added to thewater. pH of the water was in the range of 6.5 to 7.5.

    ______________________________________                                        (Stabilizer) (common to the mother liquid and replenisher)                    ______________________________________                                        1,2-Benzoylisothiazoline-3-on                                                                            0.1                                                Polyoxyethylene-p-monononylphenyl ether                                                                  0.2                                                (average degree of polymerization: 10)                                        Water ad                   1.0 l                                              pH (adjusted with ammonia water and                                                                      8.50.                                              hydrochloric acid)                                                            ______________________________________                                    

After image-exposure of the sample 101, the continuous process wasconducted until the amount of the replenished bleach fixing solution hadbecome three times as much as the amount of the mother liquid.

The running processing solution thus obtained will be referred to asprocessing solution 201. Then the color developer was prepared in thesame manner as above except that the color developing agent P-5 sulfatein the color developer was replaced with an equal molar amount of acomparative color developing agent or the color developing agent of thepresent invention as shown in Table 2, and the same continuous processas that described above was conducted to obtain running processingsolutions (processing solutions 202 to 216).

The rapidness of the process was determined as follows. After the wedgeexposure of the sample 101, it was processed running process step (a)!with a running processing solution (processing solutions 202 to 216)while the color development period was changed from 1 minute to 3minutes at intervals of 10 seconds. The optical densities of the yellow,magenta and cyan images of each of the resultant samples weredetermined. Then, after the wedge-exposure of the sample 101 conductedin the same manner as that described above, it was processed incomparative developing steps (b) described below, and the opticaldensities of the yellow, magenta and cyan images were determined in thesame manner as that described above. The density curve of the magentaimage obtained in the comparative developing steps (b) was compared withthat of each sample (obtained at intervals of 10 seconds as describedabove), and the processing time for the color development in which theequal or higher magenta density was obtained was measured to obtain theresults shown in Table 2.

Then the degree of lowering of the density of each of the yellow andcyan images was determined by using a sample which necessitated an equalprocessing time for obtaining the same magenta density. The yellow andcyan densities of each sample were determined with such an exposure thatmagenta density of 2.0 would be obtained. The densities minus (-) meanslowering of the density and plus (+) means increase thereof! are givenin Table 2 as compared with the yellow and cyan densities obtained inthe comparative developing steps (b). Further, the yellow fog density ofthe sample was determined, and the difference thereof from that obtainedin the comparative development steps (b) is shown in Table 2.

Comparative color developing agent: ##STR20## Comparative developmentsteps (b) (Processing method)

    ______________________________________                                        Step              Time      Temp.                                             ______________________________________                                        Color development 3 min 15 sec                                                                            38° C.                                     Bleaching         1 min 00 sec                                                                            38° C.                                     Bleach-fixing     3 min 15 sec                                                                            38° C.                                     Washing with water (1)                                                                          40 sec    35° C.                                     Washing with water (2)                                                                          1 min 00 sec                                                                            35° C.                                     Stabilization     40 sec    38° C.                                     Drying            1 min 15 sec                                                                            55° C.                                     ______________________________________                                    

The composition of each of the processing solutions was as follows:

    ______________________________________                                                                 (Unit: g)                                            ______________________________________                                        (Color developer)                                                             Diethylenetriaminepentaacetic acid                                                                       1.0                                                1-Hydroxyethylidene-1,1-diphosphonic acid                                                                2.0                                                Sodium sulfite             4.0                                                Potassium carbonate        30.0                                               Potassium bromide          1.4                                                Potassium iodide           1.5    mg                                          Hydroxylamine sulfate      2.4                                                4- N-ethyl-N-(β-hydroxyethyl)amino!-2-methyl-                                                       4.5                                                aniline sulfate  P-5!                                                         Water ad                   1.0    l                                           pH (with potassium hydroxide and sulfuric acid)                                                          10.05                                              (Bleaching bath)                                                              Ferric ammonium ethylenediaminetetraacetate dihydrate                                                    120.0                                              Disodium ethylenediaminetetraacetate                                                                     10.0                                               Ammonium bromide           100.0                                              Ammonium nitrate           10.0                                               Bleaching accelerator      0.005  mol                                         (CH.sub.3).sub.2 N--CH.sub.2 --CH.sub.2 --S--S--CH.sub.2 --CH.sub.2           --N(CH.sub.3).sub.2.                                                          2HCl                                                                          Ammonia water (27%)        15.0   ml                                          Water ad                   1.0    l                                           pH (adjusted with ammonia water and nitric acid)                                                         6.3                                                (Bleach-fixing bath)                                                          Ferric ammonium ethylenediaminetetraacetate dihydrate                                                    50.0                                               Disodium ethylenediaminetetraacetate                                                                     5.0                                                Sodium sulfite             12.0                                               Aqueous ammonium thiosulfate solution (700 g/l)                                                          240.0  ml                                          Ammonia water (27%)        6.0    ml                                          Water ad                   1.0    l                                           pH (adjusted with ammonia water and acetic acid)                                                         7.2                                                ______________________________________                                    

(Washing water)

Tap water was passed through a mixed bed column packed with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B; a product ofRohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400;a product of Rohm & Haas Co.) to reduce calcium and magnesium ionconcentration to 3 mg/l or below, and then 20 mg/l of sodiumisocyanurate dichloride and 0.15 g/l of sodium sulfate were added to thewater.. pH of the water was in the range of 6.5 to 7.5.

    ______________________________________                                        (Stabilizing bath)        (unit: g)                                           ______________________________________                                        Sodium p-toluenesulfinate 0.03                                                Polyoxyethylene p-monononylphenyl ether                                                                 0.2                                                 (average degree of polymerization: 10)                                        Disodium ethylenediaminetetraacetate                                                                    0.05                                                1,2,4-Triazole            1.3                                                 1,4-Bis(1,2,4-triazol-1-ylmethyl)piperazine                                                             0.75                                                Water ad                  1.0 l                                               pH                        8.5                                                 ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                               Color development time for                             Process No.                                                                           Color developing agent                                                                       obtaining given magenta density                        ______________________________________                                        201     P-5            2 min 50 sec                                           202     Comp. compound-1                                                                             2 min 20 sec                                           203     Comp. compound-2                                                                             2 min 10 sec                                           204     Comp. compound-3                                                                             2 min 10 sec                                           205     Comp. compound-4                                                                             2 min 10 sec                                           206     Comp. compound-5                                                                             2 min 20 sec                                           207     D-2            2 min 10 sec                                           208     D-7            2 min 10 sec                                           209     D-59           2 min 00 sec                                           210     D-60           2 min 00 sec                                           211     D-61           2 min 00 sec                                           212     D-70           2 min 00 sec                                           213     D-86           2 min 00 sec                                           214     D-126          2 min 10 sec                                           215     D-156          2 min 00 sec                                           216     D-160          2 min 10 sec                                           ______________________________________                                                                     Difference                                               Difference in                                                                            Difference in                                                                           in yellow                                        Process No.                                                                           yellow density                                                                           cyan density                                                                            fog density                                                                           Remarks                                  ______________________________________                                        201     +0.04      -0.02     +0.02   Comp. Ex.                                202     -0.60      -0.32     +0.27   Comp. Ex.                                203     -0.77      -0.49     +0.30   Comp. Ex.                                204     -0.85      -0.46     +0.22   Comp. Ex.                                205     -0.40      -0.53     +0.32   Comp. Ex.                                206     -0.60      -0.72     +0.48   Comp. Ex.                                207     -0.10      -0.02     +0.11   Invention                                208     0          +0.07     +0.10   Invention                                209     +0.25      +0.02     +0.12   Invention                                210     +0.10      +0.04     +0.14   Invention                                211     +0.14      +0.08     +0.10   Invention                                212     0          -0.01     +0.02   Invention                                213     +0.09      +0.06     +0.13   Invention                                214     -0.12      -0.05     +0.11   Invention                                215     +0.20      +0.06     +0.13   Invention                                216     +0.18      +0.10     +0.12   Invention                                ______________________________________                                    

It is apparent from Table 2 that with the color developing agent of thepresent invention or each of the comparative compounds 1 to 5, themagenta image density can be obtained in a development process time farshorter than that necessitated when P-5 (processing solution No. 201) isused.

It will be understood that although a high rapidness can be attainedwith the comparative compounds 1 to 5, it is not easy to obtain asatisfactory yellow density or cyan density and yellow fog density ishigh when they are used.

With the color developing agent of the present invention, the yellowdensity and cyan density could be remarkably improved while the yellowfog density could be kept low.

Namely, by using the developing agent of the present invention, therapidness of the process could be increased, yellow density and cyandensity could be secured while yellow fog density could be kept low.

Example 9

The same sample 101 as that used in Example 8 was exposed. After thedevelopment by using the compound (D-62) of the present invention as thecolor developing agent in the color developer by a method which will bedescribed below, a desired gradation could be obtained in a colordevelopment time of as short as only 60 seconds. Another advantage wasthat the fog density was low. The similar results could be obtained whenthe compound (D-62) was replaced with compound (D-2), (D-7), (D-59) or(D-60). Development steps and compositions of processing liquids:

    ______________________________________                                        Step               Temp.   Time                                               ______________________________________                                        Color development  45° C.                                                                         60 sec                                             Bleach-fixing      45° C.                                                                         60 sec                                             Washing with water (1)                                                                           40° C.                                                                         15 sec                                             Washing with water (2)                                                                           40° C.                                                                         15 sec                                             Washing with water (3)                                                                           40° C.                                                                         15 sec                                             Stabilization      40° C.                                                                         15 sec                                             Drying             80° C.                                                                         30 sec                                             ______________________________________                                    

The washing with water was conducted with three tanks by counter-currentmethod from (3) to (1).

Liquid composition:

    ______________________________________                                        (Color developer)      Mother liquid (g)                                      ______________________________________                                        Diethylenetriaminepentaacetic acid                                                                   4.0                                                    1-Hydroxyethylidene-1,1-diphosphonic acid                                                            3.0                                                    Sodium sulfite         4.0                                                    Potassium carbonate    50.0                                                   Potassium bromide      4.0                                                    Potassium iodide       1.3      mg                                            Hydroxylamine sulfate  4.0                                                    Color developing agent (D-62.naphthalene-                                                            22.8                                                   1,5-disulfonate)                                                              Water ad               1.0      l                                             pH (adjusted with potassium hydroxide and                                                            10.05                                                  sulfuric acid)                                                                ______________________________________                                        (Bleach-fixing bath)   (unit: mol)                                            ______________________________________                                        Chelating agent represented by formula A                                                             0.17                                                   Ferric nitrate nonahydrate                                                                           0.15                                                   Ammonium thiosulfate   1.25                                                   Ammonium sulfite       0.10                                                   M-carboxybenzenesulfinic acid                                                                        0.05                                                   Water ad               1.0      l                                             pH (adjusted with acetic acid and ammonia)                                                           5.8                                                    ______________________________________                                    

(Washing water)

Tap water was passed through a mixed bed column packed with an H-typestrongly acidic cation exchange resin (Amberlite IR-120B; a product ofRohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400;a product of Rohm & Haas Co.) to reduce calcium and magnesium ionconcentration to 3 mg/l or below, and then 20 mg/l of sodiumisocyanurate dichloride and 0.15 g/l of sodium sulfate were added to thewater. pH of the water was in the range of 6.5 to 7.5.

    ______________________________________                                        (Stabilizing bath)       Mother liquid (g)                                    ______________________________________                                        1,2-Benzoisothiazoline-3-on                                                                            0.1                                                  Polyoxyethylene p-monononylphenyl ether                                                                0.2                                                  (average degree of polymerization: 10)                                        Water ad                 1.0 l                                                pH (adjusted with ammonia water and                                                                    8.50                                                 hydrochloric acid)                                                             ##STR21##                                                                    ______________________________________                                    

Example 10

The same sample 101 as that used in Example 8 was exposed and thenprocessed with the color developing agent D-33 or D-144 in the colordeveloper by process Nos. 211-213. The image fastness of the samples ofa magenta density of 2.0 were examined to find that an excellent imagefastness was obtained with the compounds of the present invention.

Example 11

A sample 301 in Example 3 of J. P. KOKAI No. Hei 5-188550 was exposedand then developed by the same method as that described in thatspecification except that the color developing agent in the colordeveloper was replaced with an equimolar amount of the color developingagent (D-2), (D-59), (D-60), (D-62), (D-70), (D-86) or (D-150) of thepresent invention. The development time could be reduced, the fogdensity was low, and the difference among the magenta density, yellowdensity and cyan density was only slight favorably.

When the compound of the present invention is used as the colordeveloping agent, the process can be rapidly conducted, an image havingsufficient yellow, magenta and cyan image densities and a low fogdensity can be obtained.

What is claimed is:
 1. A color image-forming method which comprises thesetup of developing an image-exposed silver halide color photographicphotosensitive material in the presence of an aniline compoundrepresented by the following general formula (I): ##STR22## wherein R¹represents a hydrogen atom or substituent, R²,represents a substituent,Z represents a substituted or unsubstituted ethylene group orsubstituted or unsubstituted trimethylene group, n represents an integerof 2 to 8, and m represents 0 or an integer of 1 to 3, and when m is 2or larger, R² 's may be the same or different from each other.
 2. Themethod of claim 1 wherein n represents 2 to
 5. 3. The method of claim 1wherein R¹ represents a hydrogen atom or substituent having 1 to 20carbon atoms, R² represents a substituent having 0 to 20 carbon atoms,and Z represents a substituted or unsubstituted ethylene group orsubstituted or unsubstituted trimethylene group, each group of which has2 to 20 carbon atoms.
 4. The method of claim 1 wherein R¹ represents ahydrogen atom or substituent having 1 to 20 carbon atoms selected fromthe group consisting of alkyl groups, aryl groups and heterocyclicgroups, R² represents a substituent having 1 to 20 carbon atoms selectedfrom the group consisting of alkyl, alkoxy, carbamoyl, sulfamoyl andureido groups, and Z represents a substituted or unsubstituted ethylenegroup or substituted or unsubstituted trimethylene group, each group ofwhich has 2 to 20 carbon atoms wherein a substituent in the substitutedethylene group or substituted trimethylene group is selected from thegroup consisting of hydroxyl, alkyl, carboxyl, acylamino, ureido,alkoxycarbonylamino, sulfonylamino, carbamoyl, acyloxy and carbamoyloxygroups.
 5. The method of claim 1 wherein R¹ represents a hydrogen atomor substituent having 1 to 8 carbon atoms, R² represents a substituenthaving 1 to 3 carbon atoms, Z represents a substituted or unsubstitutedethylene group or substituted or unsubstituted trimethylene group, eachgroup of which has 2 to 6 carbon atoms, and m represents 0 or
 1. 6. Themethod of claim 1 wherein R¹ represents a hydrogen atom or substituenthaving 1 to 8 carbon atoms selected from the group consisting of alkylgroups, aryl groups and heterocyclic groups, R² represents a substituenthaving 1 to 3 carbon atoms selected from the group consisting of alkyl,alkoxy, carbamoyl, sulfamoyl and ureido groups, Z represents asubstituted or unsubstituted ethylene group or substituted orunsubstituted trimethylene group, each group of which has 2 to 6 carbonatoms wherein a substituent in the substituted ethylene group orsubstituted trimethylene group is selected from the group consisting ofhydroxyl, alkyl and carboxyl groups, and m represents 0 or
 1. 7. Themethod of claim 1 wherein R¹ represents a hydrogen atom or alkyl grouphaving 1 to 8 carbon atoms, R² represents a substituent having 1 to 3carbon atoms selected from the group consisting of alkyl and alkoxygroups, Z represents a substituted or unsubstituted ethylene group orsubstituted or unsubstituted trimethylene group, each group of which has2 to 6 carbon atoms wherein a substituent in the substituted ethylenegroup or substituted trimethylene group is selected from the groupconsisting of hydroxyl, alkyl and carboxyl groups, and m represents 0or
 1. 8. The method of claim 1 wherein R¹ represents a hydrogen atom oralkyl group having 1 to 3 carbon atoms, R² represents a substituenthaving 1 to 3 carbon atoms selected from the group consisting of alkyland alkoxy groups, Z represents a substituted or unsubstituted ethylenegroup or substituted or unsubstituted trimethylene group, each group ofwhich has 2 to 6 carbon atoms wherein a substituent in the substitutedethylene group or substituted trimethylene group is selected from thegroup consisting of hydroxyl, alkyl and carboxyl groups, and mrepresents 0 or
 1. 9. A color image-forming method which comprises thesetup of developing an image-exposed silver halide color photographicphotosensitive material in the presence of an aniline compoundrepresented by the following general formula (I-a): ##STR23## wherein R¹represents a hydrogen atom or alkyl group having 1 to 3 carbon atoms,R²² represents a hydrogen atom, alkyl or alkoxy group having 1 to 3carbon atoms, Z represents a substituted or unsubstituted ethylene groupor substituted or unsubstituted trimethylene group, each group of whichhas 2 to 6 carbon atoms wherein a substituent in the substitutedethylene group or substituted trimethylene group is selected from thegroup consisting of hydroxyl, alkyl and carboxyl groups, and nrepresents an integer of 2 to 5.